TWI643891B - Use of mono-substituted succinic anhydride - Google Patents

Abstract

The present invention relates to at least one monosubstituted succinic anhydride reducing the decomposition of the polymer during processing or prior to extruding a polymer composition comprising polylactic acid as a polymer component and at least one material comprising calcium carbonate as a filler. Or the use of reducing the melt flow rate of such extruded polymers and a polymer for reducing decomposition of the polymer during processing and reducing the inclusion of polylactic acid as a polymer component and at least one material comprising calcium carbonate as a filler A method of the melt flow rate of a composition; the use of a polymer composition obtainable by a process comprising the steps of: a) providing at least one polylactic acid as a polymer component, and b) providing at least one material comprising calcium carbonate as a filler, c) providing at least one monosubstituted succinic anhydride and d) contacting the components of a), b) and c) in any order and e) pressing the contacting components of step d); An article comprising a polymer composition obtainable by the foregoing method.

Description

 Use of monosubstituted succinic anhydride  

This invention relates to the use of monosubstituted succinic anhydrides associated with extrusion of polymer compositions and to a process for reducing polymer decomposition during processing.

Many products are now made of plastic because they are lighter, stronger, easier to handle and less prone to breakage. These products are usually disposable items or products that are used only once. Most of these plastic articles are made of various synthetic resins and thus do not have any biodegradability. For example, a plastic bag made of polyvinyl chloride cannot be biodegraded by the action of microorganisms, but needs to be burned in a waste incineration plant. In addition, such plastic bags are often blindly discarded in nature and may remain semi-permanently in the soil without undergoing any chemical decomposition and often pose a serious threat to animal, human health and safety and the environment.

Over the years, attempts have been made to improve this situation by replacing plastic materials with other different materials, and in particular by biodegradable polymers. Biodegradable polymers are a specific type of polymer that decomposes after its intended purpose to produce natural by-products such as gases, water, biomass, and inorganic salts. These polymers were found to be made in a natural and synthetic manner and consist mostly of ester, guanamine and ether functional groups. Its characteristics and decomposition mechanism are determined by its precise structure. Such products and materials have been known in the prior art for many years. For example, biodegradable polyhydroxyalkanoate copolymers and plastic articles comprising such copolymers are disclosed in WO 95/20615 in. The aforementioned copolymers are compostable and can therefore be processed in composting equipment. Other biodegradable plastics are known in the prior art according to, for example, WO 2013/169174 or according to US 2014/0134380.

Another known biodegradable polymer is polylactic acid or polylactide (PLA). PLA is a biodegradable thermoplastic aliphatic polyester derived from renewable resources such as corn starch, tapioca root, tapioca chips or tapioca starch or sugar cane. Due to the chiral nature of lactic acid, there are several different forms of polylactide. For example, poly-L-lactide (PLLA) is composed of L,L-lactide ( A product resulting from the polymerization of L-lactide. In 2010, PLA had the second highest consumption in any bioplastic in the world. However, the manufacture of such biodegradable polymers is often extremely difficult and expensive.

It is known in the prior art to incorporate particulate fillers into polymeric materials in order to secure the polymers and materials and to modify the properties of the polymers. By incorporating such a filler, less polymer is used, and thus, incorporation of the filler into the polymer composition can cause a decrease in the polymer material. Therefore, the final price of the polymer product can be reduced. In addition, fillers are commonly used to modify and/or modify the properties of polymeric materials. For example, a filler is added to change the color of the polymer. Alternatively, fillers may be added to modify the chemical and mechanical properties of the polymer, such as changing the softening temperature, Young's modulus, impact strength or tensile strength.

As noted above, the filler is a discontinuous particle that is added to a plastic-like material to reduce the consumption of the more expensive binder material or to improve some of the properties of the blended material. Among the most important fillers, calcium carbonate has the largest market share and is mainly used in the plastics field.

Materials comprising biodegradable polymers such as polylactic acid and fillers such as calcium carbonate are described in various documents. For example, WO 2013/190274 A2 relates to compositions comprising biopolymers and particulate mineral fillers. The biopolymer can be polylactic acid and the particulate mineral filler comprises calcined clay that enhances the biodegradability of such biopolymers.

WO 2012/094758 A1 relates to a polylactic acid resin composition comprising a chain mobility additive and a mineral filler. Examples of mineral fillers include talc, ceria, citrate, calcium carbonate, calcium sulfate, mica, apatite, kaolin, and combinations thereof.

WO 2012/018327 relates to a high heat resistant polymer composition comprising poly(lactic acid) and a method of producing the same high heat resistant polymer composition. The polymer composition comprises poly(lactic acid), an aliphatic polyester, and an organically coated calcium carbonate.

WO 2015/185533 relates to a polymer composition comprising at least 20.0% by weight, based on the total weight of the polymer composition, of at least one biodegradable polymer resin; based on the total weight of the polymer composition 0.1% to 20.0% by weight of at least one polyolefin selected from the group consisting of polyethylene and/or polypropylene; and 5.9% by weight to 60.0% by weight, based on the total weight of the polymer composition, of an inorganic filler material Dispersed in at least one polyolefin and at least one biodegradable polymer resin. The filler material can be a basic inorganic filler material.

WO 2010/001268 A2 relates to a biodegradable encapsulating film, wherein the film comprises a blend comprising at least one thermoplastic starch in an amount of from about 10% to about 60% by weight of the blend; at least one poly Lactic acid in an amount of from about 1% by weight to about 30% by weight of the blend; at least one aliphatic-aromatic copolyester in an amount of from about 20% by weight to about 70% by weight of the blend; and at least one filler , in an amount of from about 1% by weight to about 25% by weight of the blend, wherein the ratio of the total weight percent of the aliphatic-aromatic copolyester and the thermoplastic starch to the total weight percent of the polylactic acid and the filler is from about 1 to about 10.

EP 2 554 358 A1 relates to a biodegradable moisture permeable and waterproof membrane comprising polylactic acid and an inorganic filler. The inorganic filler is selected from the group consisting of calcium carbonate, barium carbonate, calcium sulfate, barium sulfate, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, magnesium oxide, titanium oxide, zinc oxide, cerium oxide, and talc.

US 2012/0288650 A1 relates to a biodegradable polyester film comprising: i) from 7 to 100% by weight, based on the total weight of component i to component ii, based on an aliphatic dicarboxylic acid and/or Or a biodegradable polyester of an aromatic dicarboxylic acid and an aliphatic dihydroxy compound; ii) from 0% to 25% by weight, based on the total weight of component i to component ii; From 10% to 25% by weight, based on the total weight of component v, of calcium carbonate; iv) from 3% to 15% by weight, based on the total weight of component i to component v, of talc; From 0 to 1% by weight, based on the total weight of component i to component v, of a copolymer containing an epoxy group and based on styrene, acrylate and/or methacrylate; vi) from component i to group 0% to 2% by weight of 2-(4,6-bisbiphenyl-4-yl-1,3,5-three, based on the total weight of v 2-yl)-5-(2-ethyl-(n)-hexyloxy)phenol.

When calcium carbonate is incorporated into a polymer composition comprising polylactic acid, the general deficiencies observed are a reduction in the mechanical properties or rheology of such polymer compositions. Incorporation of calcium carbonate into biodegradable polymers such as polylactic acid will in particular result in higher melt flow rates. This means that the polymer becomes more fluid after heating, which indicates a decrease in the molecular weight of the polymer or hydrolysis of the polymer. If the polymer becomes too liquid/liquid too strong, this represents a problem or deficiencies in polymer processing not only in conventional processing but also during the recycling process.

Therefore, there is still a need in the art to solve the above technical problems and in particular to improve the thermal stability and processability of a polymer composition comprising polylactic acid as a polymer component and a material comprising calcium carbonate as a filler at a high temperature. Sexual technical solutions. In addition, there is still a need for a polymer composition comprising modified lactic acid as a polymer component and a material comprising calcium carbonate as a filler having improved mechanical properties and in particular having a reduced melt flow rate.

Accordingly, it is an object of the present invention to provide a technique for improving the stability, particularly thermal stability, of a polymer composition comprising polylactic acid as a polymer component and a material comprising calcium carbonate as a filler, particularly during processing. solution. Another object is to promote the processability of a polymer composition comprising polylactic acid as a polymer component and a material comprising calcium carbonate as a filler during processing, especially at elevated temperatures. Another object of the present invention is to improve the mechanical properties, especially the melt flow rate, of a polymer composition comprising polylactic acid as a polymer component and a material comprising calcium carbonate as a filler.

The foregoing and other objects are solved by the subject matter as defined in the technical solution 1 herein.

Advantageous embodiments of the invention are defined in the sub-section of the corresponding claims.

1 shows a graph of the values of the melt flow rate for CE1 and an embodiment having a loading of 20 pph of filler; FIG. 2 shows a graph of the values of the melt flow rate of CE1 and an embodiment having a loading of 10 pph of filler; 3 shows a graph of the values of the tensile strain at break of Comparative Example CE1 to Comparative Example CE5 and Inventive Example E1 to Inventive Example E5.

According to one aspect of the invention, the polylactic acid is included as a polymer component in the compounding And at least one monosubstituted succinic anhydride is used before or during the polymer composition comprising at least one material comprising calcium carbonate as a filler to reduce polymer decomposition during processing and/or according to DIN EN ISO 1133-1:2011 (procedure A, 2 , 16 kg, 210 ° C, granules, as compared to the same polymer composition that has been treated in the same manner in the absence of at least one monosubstituted succinic anhydride (ie, in the absence of at least one monosubstituted succinic anhydride) The melt flow rate of such compounded polymer compositions is reduced by at least 10%.

The present inventors have surprisingly found that, according to the present invention, when at least one monosubstituted succinic anhydride is used before or during the compounding of the polymer composition, polymerization comprising polylactic acid as a polymer component and a material comprising calcium carbonate as a filler The stability of the composition of the composition, especially the thermal stability, can be significantly improved. Furthermore, the inventors have surprisingly found that the workability of the polymer composition can be promoted when at least one monosubstituted succinic anhydride is used before or during the compounding of the polymer composition. Further, according to the present invention, the mechanical properties of the polymer composition comprising polylactic acid as a polymer component and a material containing calcium carbonate as a filler, and particularly the melt flow rate, can be improved. In particular, this is achieved by using at least one monosubstituted succinic anhydride before or during the compounding of the polymer composition.

According to another aspect of the invention, there is provided a method for reducing polymer decomposition during processing and/or measuring according to DIN EN ISO 1133-1:2011 (procedure A, 2, 16 kg, 210 ° C, particles), and lack thereof Melt flow of a polymer composition comprising polylactic acid as a polymer component and at least one material comprising calcium carbonate as a filler, compared to the same polymer composition of at least one monosubstituted succinic anhydride which has been treated in the same manner A method of reducing the rate by at least 10%, the method comprising: a) providing at least one polylactic acid as a polymer component, and b) providing at least one material comprising calcium carbonate as a filler, and c) providing at least one monosubstituted succinic anhydride d The components of a), b) and c) are contacted in any order, and e) the contact components of step d) are compounded.

According to another aspect of the present invention, there is provided a use of a polymer composition obtainable by a process comprising the steps of a) providing at least one polylactic acid as a polymer component, and b) providing at least one calcium carbonate comprising a material as a filler, and c) providing at least one monosubstituted succinic anhydride d) contacting the components a), b) and c) in any order, and e) compounding the contact component of step d), a sanitary product , pharmaceutical and health products, filter products, geotextile products, agricultural and horticultural products, clothing, footwear and luggage products, household and industrial products, packaging products, construction products and the like.

According to another aspect of the present invention, there is provided an article comprising a polymer composition obtainable by a process comprising the steps of: a) providing at least one polylactic acid as a polymer component, and b) providing at least one a material comprising calcium carbonate as a filler, and c) providing at least one monosubstituted succinic anhydride d) contacting the components of a), b) and c) in any order, and e) compounding the contacting component of step d) The product is selected from the group consisting of hygiene products, pharmaceutical and health care products, filter products, geotextile products, agricultural and horticultural products, clothing, footwear and luggage products, household and industrial products, packaging products, construction Products and similar.

Advantageous embodiments of the invention are defined in the sub-section of the corresponding claims.

According to one embodiment of the invention, the at least one monosubstituted succinic anhydride consists of a succinic anhydride monosubstituted by a group selected from the group consisting of a straight chain, a branched chain, an aliphatic group, and a cyclic group having a C2 in the substituent. To C30, and in the case of a branched chain group, C3 to C30, preferably C3 to C25 and most preferably the total amount of carbon atoms of C4 to C20.

According to another embodiment of the invention, the at least one monosubstituted succinic anhydride is at least one alkyl monosubstituted succinic anhydride, preferably selected from the group consisting of at least one alkyl monosubstituted succinic anhydride: ethyl succinic anhydride, propyl Succinic anhydride, butyl succinic anhydride, triisobutyl succinic anhydride, pentyl succinic anhydride, hexyl succinic anhydride, heptyl succinic anhydride, octyl succinic anhydride, decyl succinic anhydride, decyl succinic anhydride, dodecyl succinic anhydride, Hexadesuccinic anhydride, octadecyl succinic anhydride, and mixtures thereof; and/or at least one alkenyl monosubstituted succinic anhydride, preferably selected from the group consisting of at least one alkenyl monosubstituted succinic anhydride: vinyl succinic anhydride, Propylene succinic anhydride, butenyl succinic anhydride, triisobutenyl succinic anhydride, pentenyl succinic anhydride, hexenyl succinic anhydride, heptenyl succinic anhydride, octenyl succinic anhydride, nonenyl succinic anhydride, nonenyl Succinic anhydride, dodecenyl succinic anhydride, hexadecenyl succinic anhydride, octadecyl succinic anhydride, and mixtures thereof.

According to another embodiment of the invention, at least one monosubstituted succinic anhydride is used prior to compounding the polymer composition, since at least one monosubstituted succinic anhydride and/or its salt-containing reaction product is present in at least one material comprising calcium carbonate on the surface.

According to another embodiment of the present invention, at least one monosubstituted succinic anhydride is used during compounding of the polymer composition because at least one monosubstituted succinic anhydride is mixed with polylactic acid as a polymer component and at least one comprises carbonic acid. The calcium material is contacted as a polymer composition of the filler.

According to another embodiment of the invention, the at least one monosubstituted succinic anhydride and/or its salt-containing reaction product is present in an amount of at least 0.1% by weight, based on the total dry weight of at least one filler material comprising calcium carbonate, preferably An amount of from 0.1 wt% to 4.0 wt%, more preferably from 0.1 wt% to 3.0 wt%, even more preferably from 0.2 wt% to 2.0 wt%, even more preferably from 0.3 wt% to 1.5 wt% And it is preferably present in the polymer composition in an amount of from 0.4% by weight to 1.2% by weight.

According to another embodiment of the invention, the polymer component consists solely of polylactic acid.

According to another embodiment of the invention, the at least one monosubstituted succinic anhydride and/or its salt-containing reaction product is present in an amount of at least 0.005 wt%, preferably from 0.01 wt% to 5.0 wt%, based on the total weight of the polymer component The amount of %, more preferably from 0.02 wt% to 1.0 wt%, even more preferably from 0.03 wt% to 0.8 wt%, even more preferably from 0.05 wt% to 0.5 wt% and most preferably from 0.07 wt% An amount of from % to 0.3% by weight is present in the polymer composition.

According to another embodiment of the invention, the material comprising calcium carbonate is selected from the group consisting of ground calcium carbonate, preferably marble, limestone, dolomite and/or chalk; precipitated calcium carbonate, preferably hexagonal calcite, calcite and / or aragonite; and mixtures thereof, more preferably, the material comprising calcium carbonate is ground calcium carbonate.

According to another embodiment of the present invention, the material comprising calcium carbonate has i) in the range of 0.1 μm to 10 μm, preferably in the range of 0.25 μm to 7 μm, more preferably in the range of 0.5 μm to 5 μm, and most preferably 0.7 μm. a weight median particle diameter d ₅₀ value in the range of 4 μm; and/or ii) 15μm, preferably 12.5μm, better 10μm and best Top cut of 7.5μm (d _98); and / or iii) in accordance with ISO 9277: 2010 using nitrogen and the BET method of measuring, 0.5m ² / g to 150m ² / g, preferably 1m ² / g to 60m ² /g and more preferably 1.5 m ² /g to 15 m ² /g specific surface area (BET); and / or iv) 0.01 wt% to 1 wt% based on the total dry weight of at least one material comprising calcium carbonate %, preferably from 0.02% by weight to 0.5% by weight, more preferably from 0.03% by weight to 0.3% by weight and most preferably from 0.04% by weight to 0.15% by weight of residual total water content.

According to another embodiment of the present invention, the material comprising calcium carbonate is in an amount of from 0.1% by weight to 85% by weight, preferably from 3% by weight to 50% by weight, more preferably 5% by weight, based on the total weight of the polymer component. It is present in the polymer composition in an amount of up to 40% by weight and optimally in an amount of from 10% by weight to 30% by weight.

According to another embodiment of the invention, the polymer composition may comprise other additives such as color pigments, dyes, waxes, lubricants, oxidative stabilizers and/or UV stabilizers, antioxidants and other fillers such as talc.

According to another embodiment of the invention, the tensile strain at break of the polymer composition is increased by at least 40%, preferably at least 100%, more preferably at least 200, compared to the same polymer composition lacking at least one monosubstituted succinic anhydride. % and best at least 300%.

According to another embodiment of the invention, the same polymer composition phase lacking at least one monosubstituted succinic anhydride is measured according to DIN EN ISO 1133-1:2011 (procedure A, 2, 16 kg, 210 ° C, particles) The melt flow rate of the polymer composition is reduced by at least 15%, preferably by at least 20% and optimally by at least 25%.

According to another embodiment of the present invention, in the contacting step d), at least one of the materials comprising calcium carbonate of step b) is first mixed with at least one monosubstituted succinic anhydride of step c) in one or more steps with mixing. Contacting such that a treatment layer comprising at least one monosubstituted succinic anhydride and/or its salt-containing reaction product is formed on the surface of the at least one material comprising calcium carbonate of step b), and secondarily subjecting the surface treatment to mixing The material comprising calcium carbonate is contacted with polylactic acid in one or more steps.

It should be understood that for the purposes of the present invention, the following terms have the following meaning: the term "succinic anhydride" (also known as dihydro-2,5-furandione, succinic acid anhydride or amber). Succinyl oxide has an acid anhydride of the formula C ₄ H ₄ O ₃ and is succinic acid and is known by CAS number 108-30-5.

In the meaning of the present invention, the term "mono-substituted succinic anhydride" means a succinic anhydride in which a hydrogen atom is substituted with another substituent.

In the meaning of the present invention, the term "salty reaction products of at least one mono-substituted succinic anhydride" means one or more filler materials comprising calcium carbonate. A product obtained by contacting a monosubstituted succinic anhydride. The salt-containing reaction products are formed between a monosubstituted succinic acid formed from the applied mono-substituted succinic anhydride and a reactive molecule at the surface of the filler material comprising calcium carbonate.

According to the invention, the term "compounding" means mixing and/or blending at least one polymer component with at least one additive, such as a filler material comprising calcium carbonate in a molten or softened state, in order to achieve A homogeneous blend of different materials to prepare a polymer or plastic formulation. The dispersion and distribution mixing is carried out at a temperature at which the polymer component is in a molten or softened state, but the temperature is less than the decomposition temperature. The compounding method is known to the skilled person, for example compounding can be carried out by extrusion, for example by means of a twin-screw extruder or a co-kneader.

As used herein, the term "polymer" generally includes homopolymers and copolymers such as block, graft, random and alternating copolymers, as well as blends and variants thereof. The polymer may be an amorphous polymer, a crystalline polymer or a semi-crystalline polymer, that is, a polymer comprising crystalline and amorphous moieties. Crystallinity is indicated as a percentage and can be determined by differential scanning calorimetry (DSC). The amorphous polymer may be characterized by its glass transition temperature and the crystalline polymer may be characterized by its melting point. Semi-crystalline polymers may be characterized by their glass transition temperature and/or their melting point.

In the meaning of the present invention, the term "glass transition temperature" refers to the temperature at which glass transition occurs, and the glass is converted to self-hardening in an amorphous material (or in an amorphous region within a semi-crystalline material). A relatively brittle state to a reversible transition in a molten or rubbery state. The glass transition temperature is always below the melting point of the crystalline state of the material, if any. In the meaning of the present invention, the term "melting point" means the temperature at which a solid changes its state from a solid to a liquid at atmospheric pressure. The solid phase and the liquid phase exist in equilibrium at the melting point. The glass transition temperature and melting point were determined by ISO 11357 at a heating rate of 10 ° C/min.

The term "bio-degradable" polymer refers to a polymer that can be decomposed and treated by means of bacteria or other living organisms such as fungi.

According to the present invention, the term "polymer composition" means a composition comprising at least one polylactic acid as a polymer component and at least one material comprising calcium carbonate as a filler.

According to the invention, the term "polylactic acid" refers to a polymer comprising formula I as a repeating unit.

Lactic acid is chiral and therefore refers to two optical isomers. One is known as L-(+)-lactic acid or ( S )-lactic acid, and the other (mirror image) is D-(-)-lactic acid or ( R )-lactic acid. A mixture of two optical isomers in equal amounts is referred to as DL-lactic acid or racemic lactic acid. Due to this chirality, different types of polylactic acid are known, such as poly-L-lactic acid (PLLA), poly-D-lactic acid (PDLA), and poly-DL-lactic acid (Poly). -DL-lactic Acid; PDLLA).

For the purposes of the present invention, the term "calcium carbonate-comprising filler material" or "calcium carbonate-comprising material" means a filler comprising calcium carbonate. The material has a total dry weight of at least 60% by weight and preferably at least 80% by weight of calcium carbonate.

In the meaning of the present invention, "Ground calcium carbonate (GCC)" is obtained from a natural source such as limestone, marble or chalk and is subjected to wet and/or dry treatment, for example by means of a cyclone or classifier ( Calcium carbonate treated such as grinding, sieving and/or fractionation.

In the meaning of the present invention, "precipitated calcium carbonate (PCC)" is generally precipitated by the reaction of carbon dioxide and calcium hydroxide (slaked lime) in an aqueous environment or precipitated from water by calcium and carbonate. The synthetic material obtained. Further, the precipitated calcium carbonate may be, for example, a product obtained by introducing calcium and carbonate, calcium chloride and sodium carbonate in an aqueous environment. PCC can be in the form of hexagonal calcite, calcite or aragonite. The PCC is described, for example, in EP 2 447 213 A1, EP 2 524 898 A1, EP 2 371 766 A1, EP 2 840 065 A1 or WO 2013/142473 A1.

The term "dry" or "dried" material is understood to mean a material having between 0.001 wt% and 0.5 wt% water, based on the total weight of the material comprising calcium carbonate. % water (equal to "moisture content" is determined by gravity. In the sense of the present invention, "drying" means heating until the water content of the material comprising calcium carbonate is in a material comprising calcium carbonate. The total weight of the weight ranges from 0.001% by weight to 0.5% by weight.

Herein, the "particle size" of a particulate material, such as a material containing calcium carbonate, is described _by the distribution of its particle diameter dx . Wherein the value d _x represents a diameter with respect to which x % by weight of the particles has a diameter smaller than d _x . This means, for example, that the d ₂₀ value is a particle diameter at which 20% by weight of all particles are smaller than the particle diameter. The d ₅₀ value is therefore the weight median particle size, i.e. 50% by weight of all particles are larger than this particle size and the remaining 50% by weight is smaller than this particle size. For purposes of this invention, unless otherwise indicated, the particle diameter is defined as the weight median particle diameter d _50. The d ₉₈ value is a particle diameter at which 98% by weight of all the particles are smaller than the particle diameter. The d ₉₈ value is also known as "top cut." By particle size is measured using Sedigraph ^TM 5100 Micromeritics Instrument Company or Sedigraph ^TM 5120 instrument. Methods and apparatus are known to the skilled artisan and are commonly used to determine the particle size of fillers and pigments. The measurement was carried out in an aqueous solution of 0.1 wt% Na ₄ P ₂ O ₇ . The sample was dispersed using a high speed stirrer and sonicated.

Within the meaning of the present invention, the "specific surface area (SSA)" of a material comprising calcium carbonate is defined as the surface area of the material comprising calcium carbonate divided by its mass. As used herein, the specific surface area was measured by nitrogen adsorption using a BET isotherm (ISO 9277:2010) and indicated in m ² /g.

For the purposes of the present invention, the term "viscosity" or "Brookfield viscosity" refers to the Brookfield viscosity. For this purpose, the Brookfield viscosity is measured by a Brookfield DV-III supervisometer using a suitable spindle of the Brookfield RV-spindle at 100 rpm at 24 °C ± 3 °C and in mPa. s indicate. After the spindle was inserted into the sample, the measurement was started at a constant rotational speed of 100 rpm. The reported Brinell viscosity values are values displayed 60 seconds after the start of the measurement. Based on their technical knowledge, the technician will select the spindle from the Brookfield RV-spindle group for the viscosity range to be measured. For example, for 200mPa. s with 800mPa. For the viscosity range between s, use the No. 3 spindle for 400mPa. s with 1 600mPa. For the viscosity range between s, use the No. 4 spindle for 800mPa. s with 3 200mPa. For the viscosity range between s, use the No. 5 spindle for 1 000mPa. s with 2 000 000 mPa. For the viscosity range between s, the No. 6 spindle can be used, and for 4 000 mPa. s with 8 000 000 mPa. For the viscosity range between s, the No. 7 spindle can be used.

For the purposes of this application, a "water-insoluble" material is defined as a material that is 100 g of this material mixed with 100 g of deionized water and filtered through a filter having a pore size of 0.2 μm at 20 ° C for recycling. In the case of a liquid filtrate, less than or equal to 0.1 g of recovered solid material is provided after evaporating 100 g of the liquid filtrate at ambient pressure at 95 ° C to 100 ° C. A "water-soluble" material is defined as the following material, when 100 g of this material is mixed with 100 g of deionized water and filtered through a filter having a pore size of 0.2 μm at 20 ° C to recover the liquid filtrate at 95 ° C to More than 0.1 g of recovered solid material is provided after evaporation of 100 g of the liquid filtrate at ambient pressure at 100 °C.

In the meaning of the present invention, "suspension" or "slurry" includes insoluble solids and solvents or liquids, preferably water, and optionally other additives, and usually contains a large amount of solids, and thus It is more viscous and can have a higher density than the liquid from which it is formed.

For the purposes of the present invention, the "solids content" of a liquid composition is a measure of the amount of material remaining after all solvents or water have evaporated.

According to the present invention, "melt flow rate" or "MFR", "melt mass flow rate", "melt flow index" or "melt index (melt) Index) is a measure of the ease of flow of molten plastic and is expressed in g/10 min. Typical melt flow instruments are compact and easy to use and are known to the skilled person. According to the invention, the melt flow rate is measured according to DIN EN ISO 1133-1:2011 by using program A. The pelletized polymer composition was fluidized by heating to 210 ° C and forced to flow out of the cylinder through a capillary die having an inner diameter of 2.095 mm and a length of 8 mm. The squeeze piston has a static load at 2.16 kg. MFR is obtained under standard conditions.

According to the invention, "tensile strain at break" or "ultimate tensile strength" is a measure of the force per unit area (MPa or psi) required to break the material in this manner. Typical instruments for measuring tensile strain at break are known to the skilled person. The tensile strain at break can be measured according to DIN EN ISO 527:2012 and other test methods can also be used. According to the invention, the tensile strain at break is measured according to DIN EN ISO 527-2/1BA/50:2012, which means that the sample is pulled apart at a speed of 50 mm/min during the test. The sample of the present invention has a geometric structure of 1 BA, except that the thickness of the sample is between 1.9 mm ± 2 mm and the measured length is 25 mm x 5 mm. The tensile strain at break was obtained under standard conditions.

According to the invention, the term "standard condition" means standard ambient temperature and pressure (SATP), which means a temperature of 298.15 K (25 ° C) and exactly 100000 Pa (1 bar, Absolute pressure of 14.5 psi, 0.98692 standard atmospheric pressure (atm).

Where the term "comprising" is used in the context of the specification and claims, it does not exclude other non-designated elements that have a primary or secondary functional importance. For the purposes of the present invention, the term "consisting of" is taken to mean a preferred embodiment of the term "comprising of". If a group is defined below to include at least a certain number of specific instances, it is also understood to disclose a group that is preferably only composed of such specific examples.

Whenever the terms "including" or "having" are used, they are meant to be equivalent to "comprising" as defined above.

Unless explicitly stated otherwise, when an singular noun is used, an indefinite or definite article, such as "a/an" or "the", includes the plural.

Terms such as "obtainable" or "definable" and "obtained" or "defined" are used interchangeably. This means, for example, that the term "obtaining" does not mean, unless the context clearly dictates, a specific instance that must be obtained, for example, by the sequence of steps after the term "obtaining", although the terms "acquired" or "defined" always include such limitations. As a preferred specific example.

According to the present invention, it has been found that a monosubstituted succinic anhydride can be used before or during compounding of the polymer composition to improve the stability of the polymer composition comprising polylactic acid as a polymer component and a material comprising calcium carbonate as a filler, In particular, it is thermally stable and/or promotes the processability of such polymer compositions and/or improves the mechanical properties of such polymer compositions, especially the melt flow rate. Accordingly, according to the present invention, at least one monosubstituted succinic anhydride reduces polymer decomposition during processing before or during compounding a polymer composition comprising polylactic acid as a polymer component and at least one material comprising calcium carbonate as a filler. / or according to DIN EN ISO 1133-1:2011 (Procedure A, 2.16 kg, 210 ° C, granules), compared to the same polymer composition which has been treated in the same manner in the absence of at least one monosubstituted succinic anhydride The use of reducing the melt flow rate of such compounded polymer compositions by at least 10%.

Hereinafter, details and preferred specific examples of the use of the present invention as described in the first embodiment of the present invention will be explained in more detail before or during the compounding of the polymer composition.

The polymer composition according to the present invention comprises polylactic acid as a polymer component and at least one material comprising calcium carbonate as a filler.

At least one material comprising calcium carbonate

The polymer composition of the present invention comprises at least one material comprising calcium carbonate as a filler.

The expression "at least one" of materials comprising calcium carbonate means one or more, for example two or three materials comprising calcium carbonate may be present in the polymer composition. According to a preferred embodiment, only one material comprising calcium carbonate is present in the polymer composition.

According to a preferred embodiment of the present invention, the material comprising calcium carbonate is selected from the group consisting of ground calcium carbonate (GCC), preferably marble, limestone, dolomite and/or chalk; precipitated calcium carbonate, preferably hexagonal Calcite, calcite and/or aragonite; and mixtures thereof, more preferably, at least one material comprising calcium carbonate is ground calcium carbonate.

It should be understood that natural calcium carbonate or ground calcium carbonate (GCC) is made from the naturally occurring form of calcium carbonate, from sedimentary rocks such as limestone or chalk, or from metamorphic marble, eggshells or shells. Calcium carbonate is known to exist in three types of crystalline polymorphs: calcite, aragonite and hexagonal calcite. Calcite, the most common crystalline polymorph, is considered to be the most stable crystalline form of calcium carbonate. Less common is aragonite, which has a dispersed or clustered acicular orthorhombic crystal structure. Hexagonal calcite is the rarest calcium carbonate polymorph and is generally unstable. The ground calcium carbonate is almost entirely a calcite-type polymorph, which is called a trigonal rhombohedron and represents the most stable form of the calcium carbonate polymorph. In the meaning of the present application, the term "source" of calcium carbonate refers to a naturally occurring mineral from which calcium carbonate is obtained. The source of calcium carbonate may comprise other naturally occurring components such as magnesium carbonate, aluminum citrate, and the like.

In general, the grinding of natural ground calcium carbonate can be a dry or wet milling step, and can be performed by any conventional grinding device, for example, under conditions such that the pulverization is mainly caused by impact with the secondary body, that is, in one of the following Or more implemented: ball mill, rod mill, vibrating mill, roller crusher, centrifugal impact mill, vertical bead mill, grinder, pin mill, hammer mill, mill, shredder , a chipper, a knife cutter or other such device known to the skilled person. Where the mineral comprising calcium carbonate comprises a mineral comprising wet ground calcium carbonate, it may be subjected to autogenous grinding and/or by horizontal ball milling and/or other such as known to the skilled artisan. The method is followed by a grinding step. The wet-processed ground calcium carbonate-containing mineral thus obtained can be washed and dehydrated by well-known methods, for example by flocculation, filtration or forced evaporation, prior to drying. The subsequent drying step, if desired, can be carried out in a single step (such as spray drying) or in at least two steps. It is also common for such minerals to undergo a beneficiation step (such as a flotation, bleaching or magnetization separation step) to remove impurities.

According to one embodiment of the invention, the source of natural calcium carbonate or ground calcium carbonate (GCC) is selected from the group consisting of marble, chalk, limestone, dolomite or mixtures thereof. Preferably, the source of ground calcium carbonate is marble, and more preferably is a dolomitic marble and/or a magnesitic marble. According to one embodiment of the invention, GCC is obtained by dry milling. According to another embodiment of the invention, GCC is obtained by wet milling and subsequent drying.

In the meaning of the present invention, "dolomite" is a mineral containing calcium carbonate, that is, a calcium carbonate-magnesium mineral having a chemical composition of CaMg(CO ₃ ) ₂ ("CaCO ₃ .MgCO ₃ "). Dolomite mineral contains dolomite may total weight, of at least 30.0wt% MgCO _3, preferably greater than 35.0wt%, and more preferably greater than 40.0wt% MgCO _3.

According to a specific embodiment of the invention, the calcium carbonate comprises a ground calcium carbonate. According to another embodiment of the invention, the calcium carbonate comprises a mixture of two or more than two ground calcium carbonates selected from different sources.

In the meaning of the present invention, "precipitated calcium carbonate (PCC)" is a synthetic substance which is generally precipitated by reacting carbon dioxide with lime in an aqueous environment or precipitated in water by calcium and carbonate ions. Or obtained by precipitation from a solution by combining calcium and carbonate ions (for example, CaCl ₂ and Na ₂ CO ₃ ). Other possible ways to make PCC are the lime base process, or the Solvay process, where PCC is a by-product of ammonia manufacture. Precipitated calcium carbonate exists in three major crystalline forms: calcite, aragonite and hexagonal calcite, and each of these crystalline forms has many different polymorphs (crystal habits). Calcite has a three-way structure, and its typical crystal habits are such as scalenohedral (S-PCC), rhombohedron (R-PCC), hexagonal prism, axial, colloidal (C-PCC), cuboid and prism. Shape (P-PCC). The aragonite is an orthorhombic structure, and its typical crystal habit is a bicrystal hexagonal prismatic crystal, as well as different types of elongated prismatic, curved blade, steep cone, hazelnut crystal, branched tree and coral or Worm-like form. The hexagonal calcite belongs to the hexagonal crystal system. The obtained PCC slurry can be mechanically dehydrated and dried.

According to a specific embodiment of the invention, the precipitated calcium carbonate is precipitated calcium carbonate, which preferably comprises aragonite, hexagonal calcite or calcite mineral crystal form or a mixture thereof.

According to a specific embodiment of the invention, the calcium carbonate comprises a precipitated calcium carbonate. According to another embodiment of the invention, the calcium carbonate comprises a mixture of two or more precipitated calcium carbonates selected from the different crystalline forms of precipitated calcium carbonate and the different polymorphs. For example, the at least one precipitated calcium carbonate can comprise a PCC selected from the group consisting of S-PCC and a PCC selected from the group consisting of R-PCC.

According to a preferred embodiment of the invention, the at least one material comprising calcium carbonate is ground calcium carbonate, preferably dry ground calcium carbonate. According to another preferred embodiment, the at least one material comprising calcium carbonate is marble.

It will be appreciated that the amount of calcium carbonate in the at least one filler material comprising calcium carbonate is at least 60 wt%, preferably at least 80 wt% (e.g., at least 95 wt%) based on the total dry weight of the at least one filler material comprising calcium carbonate. More preferably between 97 wt% and 100 wt% and even more preferably between 98.5 wt% and 99.95 wt%.

The at least one filler material comprising calcium carbonate is preferably in the form of a particulate material and may have a particle size distribution as is conventionally used for the type of product to be manufactured. According to a specific embodiment of the invention, the at least one filler material comprising calcium carbonate has a weight median particle diameter d ₅₀ value in the range of from 0.1 μm to 10 μm. For example, the at least one filler material comprising calcium carbonate has a weight median particle diameter d _{50 of} from 0.5 μm to 5 μm and preferably from 0.7 μm to 4 μm.

According to a specific embodiment of the present invention, at least one material comprising calcium carbonate, preferably ground calcium carbonate ( d ₉₈ ) may be 15μm. For example, the top cut ( d ₉₈ ) of at least one material comprising calcium carbonate can be 12.5 μm, preferably 10μm and best 7.5 μm.

According to another embodiment of the present invention, such as in accordance with ISO 9277: 2010 using nitrogen and the BET method of measuring, ground calcium carbonate and / or precipitated calcium carbonate of a specific surface area of 0.5m ² / g to 150m ² / g, preferably 1 m ² /g to 60 m ² /g and most preferably 1.5 m ² /g to 15 m ² /g.

Depending on at least one filler material comprising calcium carbonate, according to one embodiment, the residual total moisture content of the at least one filler material comprising calcium carbonate may be based on the total dry weight of the at least one filler material comprising calcium carbonate. 0.01 wt% to 1 wt%, preferably 0.02 wt% to 0.5 wt%, more preferably 0.03 wt% to 0.3 wt%, and most preferably 0.04 wt% to 0.15 wt%.

For example, in the case of using wet-milling and drying calcium carbonate as at least one filler material comprising calcium carbonate, the residual total water content of at least one filler material comprising calcium carbonate is preferably at least one comprising calcium carbonate. The total dry weight of the filler material is from 0.01 wt% to 1 wt%, more preferably from 0.02 wt% to 0.1 wt%, and most preferably from 0.04 wt% to 0.08 wt%. If PCC is used as the at least one filler material comprising calcium carbonate, the residual total water content of the at least one filler material comprising calcium carbonate is preferably 0.01 wt% based on the total dry weight of the at least one filler material comprising calcium carbonate. % to 1 wt%, more preferably 0.05 wt% to 0.2 wt% and most preferably 0.05 wt% to 0.15 wt%.

According to a specific embodiment of the present invention, the material comprising calcium carbonate has a range of from 0.1 μm to 10 μm, preferably from 0.25 μm to 7 μm, more preferably from 0.5 μm to 5 μm, and most preferably from 0.7 μm to 4 μm. The weight median particle diameter d ₅₀ value; 15μm, preferably 12.5μm, better 10μm and best Top cut of 7.5 μm ( d ₉₈ ); and as measured according to ISO 9277:2010 using nitrogen and BET methods, 0.5 m ² /g to 150 m ² /g, preferably 1 m ² /g to 60 m ² /g and more a specific surface area (BET) of from 1.5 m ² /g to 15 m ² /g; and from 0.01 wt% to 1 wt%, preferably from 0.02 wt% to 0.5 wt%, based on the total dry weight of at least one material comprising calcium carbonate More preferably, the residual total water content is from 0.03 wt% to 0.3 wt% and most preferably from 0.04 wt% to 0.15 wt%.

According to a specific embodiment of the present invention, at least one filler material comprising calcium carbonate is dry ground calcium carbonate, preferably marble, having a median diameter diameter d _{50 of} from 0.1 μm to 10 μm, preferably from 0.25 μm to 7 μm, more preferably 0.5. Μm to 5 μm and most preferably 0.7 μm to 4 μm, and measured according to ISO 9277 using nitrogen gas and BET method, the BET specific surface area is from 0.5 m ² /g to 150 m ² /g, preferably from 1 m ² /g to 60 m ² /g More preferably, it is 1.5 m ² /g to 15 m ² /g.

According to a preferred embodiment of the present invention, at least one filler material comprising calcium carbonate is dry ground calcium carbonate, preferably marble, having a median diameter diameter d _{50 of} from 0.7 μm to 4 μm, for example 2.6 μm, and according to ISO 9277 is measured using nitrogen gas and a BET method, and has a BET specific surface area of from 1.5 m ² /g to 15 m ² /g, for example, 2.6 m ² /g.

According to one embodiment of the invention, another surface coating is present on the surface of the material comprising calcium carbonate.

Polylactic acid

The polymer composition of the present invention comprises polylactic acid as a polymer component.

According to the invention, the term "polylactic acid" refers to a polymer comprising formula I as a repeating unit.

The lactic acid having the chemical formula CH ₃ CH(OH)CO ₂ H is an organic compound which is a naturally occurring and synthetically produced white water-soluble solid or transparent liquid. Lactic acid is chiral and therefore refers to two optical isomers. One is known as L-(+)-lactic acid or ( S )-lactic acid, and the other (mirror image) is D-(-)-lactic acid or ( R )-lactic acid. A mixture of two optical isomers in equal amounts is referred to as DL-lactic acid or racemic lactic acid. Lactic acid is hygroscopic. DL-lactic acid can be miscible with water and ethanol at temperatures above its melting point (about 17 ° C to 18 ° C). D-lactic acid and L-lactic acid have a higher melting point of 53 °C. Lactic acid is known to the skilled person and can be purchased, for example, from Sigma Aldrich, Caesar & Loretz, NatureWorks (under the trade name Biopolymer 2003D) or other known suppliers.

There are several industrial routes to make polylactic acid (PLA), which are known to the skilled person. In general, two main monomers are used to make the PLA. Option 1 is a ring-opening polymerization of a cyclic diester lactide with various metal catalysts in solution, in a melt or as a suspension. The metal-catalyzed reaction tends to cause racemization of the PLA, which reduces its stereoregularity compared to the starting material (usually corn starch). Another way to make PLA is to directly condense the lactic acid monomer at a temperature of less than 200 °C. However, this reaction produces one equivalent of water for each condensation (esterification) step, which is undesirable because water can cause chain transfer to produce low molecular weight materials. The direct condensation is therefore preferably carried out in a stepwise manner in which the lactic acid is first oligomerized into a PLA oligomer. Thereafter, polycondensation is carried out in the melt or in the form of a solution in which short oligomeric units are combined to give a high molecular weight polymer chain. Removal of water by application of vacuum or by azeotropic distillation is critical to promoting polycondensation relative to transesterification. Processes or processes for the manufacture of polylactic acid are disclosed, for example, in US 7,507,561, EP 2 607 399 or WO 2004/057008.

Due to the chirality of lactic acid, different types of polylactic acid are known, such as poly-L-lactic acid (PLLA), poly-D-lactic acid (PDLA), and poly-DL-lactic acid (PDLLA). According to a specific embodiment of the invention, the polylactic acid is PLLA. According to another embodiment of the invention, the polylactic acid is PDLA. According to another embodiment of the invention, the polylactic acid is PDLLA. According to a specific example, the polylactic acid may be composed of only one specific type of PLA or a mixture of two or more types of PLA. For example, polylactic acid can be composed of a mixture of PLLA and PDLLA. According to a preferred embodiment, the polylactic acid consists of only one specific type of PLA. The polylactic acid may be, for example, PDLLA comprising a D isomer of between 1 wt% and 10 wt%, preferably between 4 wt% and 6 wt%, based on the total weight of the polylactic acid. Polylactic acid is commercially available, for example, from NatureWorks under the trade name Biopolymer 2003D.

According to one embodiment of the invention, the polylactic acid is a copolymer of polylactic acid and at least one other monomer of the class. For example, polylactic acid is a copolymer of polylactic acid and polyethylene glycol.

According to a preferred embodiment, the polylactic acid is a homopolymer and thus consists only of the repeating units of the above formula I.

Depending on the processability and thermal history of the PLA, it may be in the form of amorphous and semi-crystalline polymers, i.e., in the form of polymers comprising crystalline and amorphous moieties. The semi-crystalline material may be transparent or opaque and white depending on its crystal structure and particle size.

According to a specific example, the PLA is amorphous. According to another embodiment, the PLA is semicrystalline, preferably, the PLA has a crystallinity of at least 20%, more preferably at least 40% and most preferably at least 50%. According to still another embodiment, the crystallinity of the PLA is from 10% to 80%, more preferably from 20% to 70% and most preferably from 30% to 60%. The degree of crystallinity can be measured by differential scanning calorimetry (DSC).

According to a specific embodiment of the present invention, the inherent viscosity of PLA is from 2 dl/g to 8 dl/g, preferably from 2.2 dl/g to 6 dl/g and more preferably from 2.8 dl/g to 4 dl/g. The term "intrinsic viscosity" as used in the context of the present invention is a measure of the ability of a polymer in solution to enhance the viscosity of the solution and is indicated in dl/g.

According to another embodiment of the present invention, the glass transition temperature T _g of the PLA is from 35 ° C to 90 ° C, preferably from 40 ° C to 70 ° C and more preferably from 45 ° C to 65 ° C.

According to a specific example of the present invention, the number average molecular weight of the PLA is from 5,000 g/mol to 200,000 g/mol, preferably from 10,000 g/mol to 100,000 g/mol and more preferably from 15,000 g/mol to 80,000 g/mol.

According to a specific example of the present invention, the specific gravity of the PLA is from 0.5 to 5, preferably from 0.7 to 4 and more preferably from 1 to 3. According to the invention, the term "specific gravity" is the ratio of the density of the PLA to the density of the reference substance; equivalently, it is the ratio of the mass of the PLA to the mass of the reference substance of the same given volume. The reference substance is water.

According to a preferred embodiment of the present invention, the polylactic acid is PDLLA comprising 4% by weight to 6% by weight of the D isomer based on the total weight of the polylactic acid. Further, PDLLA has a specific gravity of 1 to 3 and a glass transition temperature of 45 ° C to 65 ° C.

Polymer composition

The polymer composition according to the present invention comprises polylactic acid as a polymer component and at least one material comprising calcium carbonate as a filler.

According to a specific embodiment of the present invention, the material comprising calcium carbonate is in an amount of from 0.1% by weight to 85% by weight, preferably from 3% by weight to 50% by weight, more preferably from 5% by weight to the total weight of the polymer component. It is present in the polymer composition in an amount of 40% by weight and optimally in an amount of from 10% by weight to 30% by weight.

According to another embodiment of the invention, the polymer composition may comprise other additives such as color pigments, dyes, waxes, lubricants, oxidative stabilizers and/or UV stabilizers, antioxidants and other fillers such as talc. Such additives are known to the skilled person and are commercially available.

According to another embodiment of the invention, the polymer composition comprises other polymer components. For example, the polymer composition may comprise other polyesters, starch or starch derivatives, polycaprolactone (PCL), cellulosic polymers (such as cellulose acetate), polyethylene glycol, polyvinyl acetate. Ester, polyolefin (concomitant compatibilizer), polyacetal, poly(meth) acrylate, polycarbonate, high rubber content ABS (50% to 85% rubber) or mixtures thereof.

Polyesters are a class of polymers containing ester functional groups in the backbone and are typically obtained by polycondensation reactions. Polyesters can include naturally occurring polymers such as horn cortex as well as synthetic polymers such as polycarbonate or polybutyrate. The polyester may be biodegradable depending on its structure. Within the meaning of the present invention, the term "bio-degradable" relates to substances or articles which are capable of being degraded or decomposed by means of bacteria or other living organisms and thereby avoiding environmental pollution.

According to a specific example, the polyester is selected from the group consisting of polyglycolic acid, polycaprolactone, poly(ethylene adipate), polybutylene adipate, polyhydroxyalkanoate (PHA). , polyhydroxybutyrate, polyalkylene terephthalate, polyethylene terephthalate ethyl ester, poly(trimethylene terephthalate), polybutylene terephthalate, polyethylene naphthalate Or a mixture thereof or a copolymer thereof. The copolymer may be, for example, poly(butylene adipate-co-terephthalate; PBAT). Any of these polymers may be in pure form (i.e., in the form of a homopolymer) or may be modified by copolymerization and/or by adding one or more substituents to the side chain of the backbone or backbone. .

According to a specific embodiment of the invention, the polymer composition comprises polylactic acid as a polymer component and at least one other polymer component, such as one or two or three other polymer components. If the polymer composition comprises other polymer components than polylactic acid, preferably such polymers are biodegradable.

According to a specific embodiment of the invention, the ratio of polylactic acid to other polymer components present in the polymer composition is from 99:1 to 20:80, preferably 95:5, by weight of the polymer component. 50:50 and best 90:10 to 60:40.

According to a preferred embodiment, the polymer component consists solely of polylactic acid. This means that the polymer composition contains polylactic acid as the sole polymer component, and therefore, no other polymer component is present in the polymer composition.

According to another preferred embodiment of the invention, the polymer composition consists solely of the polymer component and the filler material comprising calcium carbonate. For example, the polymer composition can be composed of polylactic acid (as a polymer component), another polymer component, and a filler material comprising calcium carbonate. According to a preferred embodiment of the invention, the polymer composition consists solely of polylactic acid (as a polymer component) and at least one material comprising calcium carbonate (as a filler).

At least one monosubstituted succinic anhydride

At least one monosubstituted succinic anhydride is used in accordance with the invention.

It should be understood that the expression "at least one" monosubstituted succinic anhydride means that one or more monosubstituted succinic anhydrides may be provided in the process of the invention.

Therefore, it should be noted that at least one monosubstituted succinic anhydride may be a monosubstituted succinic anhydride. Alternatively, the at least one monosubstituted succinic anhydride can be a mixture of two or more than one monosubstituted succinic anhydrides. For example, the at least one monosubstituted succinic anhydride can be a mixture of two or three monosubstituted succinic anhydrides, such as two monosubstituted succinic anhydrides.

In one embodiment of the invention, the at least one monosubstituted succinic anhydride consists solely of one monosubstituted succinic anhydride.

According to one embodiment of the invention, the at least one monosubstituted succinic anhydride consists of succinic anhydride monosubstituted by a group selected from the group consisting of any straight chain, branched chain, aliphatic and cyclic group, which has in the substituent C2 to C30 and in the case of a branched chain group, the total amount of carbon atoms of C3 to C30.

In one embodiment of the invention, the at least one monosubstituted succinic anhydride consists of a succinic anhydride monosubstituted with a group selected from the group consisting of a straight chain, a branched chain, an aliphatic group, and a cyclic group, wherein in the substituent The total amount of carbon atoms from C3 to C25. For example, at least one monosubstituted succinic anhydride consists of a succinic anhydride monosubstituted by a group selected from the group consisting of a straight chain, a branched chain, an aliphatic group, and a cyclic group having a C4 to C20 carbon in the substituent. The total amount of atoms.

In one embodiment of the invention, the at least one monosubstituted succinic anhydride is comprised of a succinic anhydride monosubstituted by a group of linear and aliphatic groups, wherein the group has from C2 to C30, preferably C3 to C25 and the total amount of carbon atoms of C4 to C20. Additionally or alternatively, the at least one monosubstituted succinic anhydride consists of a succinic anhydride monosubstituted by a group which is a branched chain and an aliphatic group, wherein the group has a C3 to C30, preferably C3 to C25 and the total amount of carbon atoms from C4 to C20.

Thus, preferably, the at least one monosubstituted succinic anhydride consists of a succinic anhydride monosubstituted by a group which is a linear or branched alkyl group, wherein the group has a C2 to C30 in the substituent and is in the branched chain In the case of a group, the total amount of carbon atoms of C3 to C30, preferably C3 to C25 and most preferably C4 to C20.

For example, at least one monosubstituted succinic anhydride consists of a succinic anhydride monosubstituted by a group which is a linear alkyl group, wherein the group has from C2 to C30, preferably from C3 to C25 and most preferably C4 to the substituent. The total amount of carbon atoms in C20. Additionally or alternatively, the at least one monosubstituted succinic anhydride consists of a succinic anhydride monosubstituted by a group which is a branched alkyl group, wherein the group has from C3 to C30, preferably from C3 to C25 and most The total amount of carbon atoms from C4 to C20.

In the meaning of the present invention, the term "alkyl" means a straight or branched chain saturated organic compound composed of carbon and hydrogen. In other words, "alkyl monosubstituted succinic anhydride" is composed of a linear or branched saturated hydrocarbon chain containing a pendant succinic anhydride group.

In one embodiment of the invention, the at least one monosubstituted succinic anhydride is at least one linear or branched alkyl monosubstituted succinic anhydride. For example, the at least one alkyl mono-substituted succinic anhydride is selected from the group consisting of ethyl succinic anhydride, propyl succinic anhydride, butyl succinic anhydride, triisobutyl succinic anhydride, pentyl succinic anhydride, hexyl succinic anhydride Heptyl succinic anhydride, octyl succinic anhydride, mercapto succinic anhydride, mercapto succinic anhydride, dodecyl succinic anhydride, hexadecyl succinic anhydride, octadecyl succinic anhydride, and mixtures thereof.

Thus, it should be understood that, for example, the term "butylsuccinic anhydride" includes both linear and branched butyl succinic anhydrides. A specific example of a linear butyl succinic anhydride is n-butyl succinic anhydride. Specific examples of branched butyl succinic anhydride are isobutyl succinic anhydride, second butyl succinic anhydride and/or tert-butyl succinic anhydride.

Furthermore, it will be appreciated that, for example, the term "hexadecanyl succinic anhydride" encompasses both linear and branched chain hexadecanol succinic anhydride. A specific example of linear hexadecyl succinic anhydride is n-hexadecyl succinic anhydride. Specific examples of the branched chain hexadecyl succinic anhydride are 14-methylpentadecyl succinic anhydride, 13-methylpentadesyl succinic anhydride, 12-methylpentadesyl succinic anhydride, 11-methylpentadesyl succinic anhydride , 10-methylpentadecyl succinic anhydride, 9-methylpentadesyl succinic anhydride, 8-methylpentadesyl succinic anhydride, 7-methylpentadesyl succinic anhydride, 6-methylpentadesyl succinic anhydride , 5-methylpentadecyl succinic anhydride, 4-methylpentadesuccinic anhydride, 3-methylpentadesuccinic anhydride, 2-methylpentadesuccinic anhydride, 1-methylpentadesuccinic anhydride , 13-ethyltetradecyl succinic anhydride, 12-ethyltetradecyl succinic anhydride, 11-ethyltetradecyl succinic anhydride, 10-ethyltetradecyl succinic anhydride, 9-ethyltetradecyl succinic anhydride , 8-ethyltetradecyl succinic anhydride, 7-ethyltetradecyl succinic anhydride, 6-ethyltetradecyl succinic anhydride, 5-ethyltetradecyl succinic anhydride, 4-ethyltetradecyl succinic anhydride , 3-ethyltetradecyl succinic anhydride, 2-ethyltetradecyl succinic anhydride, 1-ethyltetradecyl succinic anhydride, 2-butyldodecyl succinic anhydride, 1-hexyldecyl succinic anhydride, 1 -hexyl-2-fluorenyl Succinic anhydride, 2-hexyldecyl succinic anhydride, 6,12-dimethyltetradecyl succinic anhydride, 2,2-diethyldodesuccinic anhydride, 4,8,12-trimethyltridecyl amber Anhydride, 2,2,4,6,8-pentamethylundosyl succinic anhydride, 2-ethyl-4-methyl-2-(2-methylpentyl)-heptyl succinic anhydride and/or 2 -ethyl-4,6-dimethyl-2-propyldecyl succinic anhydride.

Furthermore, it should be understood that, for example, the term "octadecanyl succinic anhydride" encompasses both linear and branched chain octadecyl succinic anhydride. A specific example of a linear octadecyl succinic anhydride is n-octadecyl succinic anhydride. Specific examples of the branched chain hexadecyl succinic anhydride are 16-methylheptadesyl succinic anhydride, 15-methylheptadesyl succinic anhydride, 14-methylheptadesyl succinic anhydride, 13-methylheptadesyl succinic anhydride , 12-methylheptadesyl succinic anhydride, 11-methylheptadesyl succinic anhydride, 10-methylheptadesyl succinic anhydride, 9-methylheptadesyl succinic anhydride, 8-methylheptadesyl succinic anhydride , 7-methylheptadesyl succinic anhydride, 6-methylheptadesuccinic anhydride, 5-methylheptadesuccinic anhydride, 4-methylheptadesuccinic anhydride, 3-methylheptadesuccinic anhydride 2-methylheptadesyl succinic anhydride, 1-methylheptadesyl succinic anhydride, 14-ethylhexadecyl succinic anhydride, 13-ethylhexadecyl succinic anhydride, 12-ethylhexadecyl succinic anhydride , 11-ethylhexadecyl succinic anhydride, 10-ethylhexadecyl succinic anhydride, 9-ethylhexadecyl succinic anhydride, 8-ethylhexadecyl succinic anhydride, 7-ethylhexadecyl succinic anhydride , 6-ethylhexadecyl succinic anhydride, 5-ethylhexadecyl succinic anhydride, 4-ethylhexadesuccinic anhydride, 3-ethylhexadecane anhydride, 2-ethylhexadecane anhydride 1-ethyl ten Succinic anhydride, 2-hexyl-dodecyl succinic anhydride, 2-heptyl-undecyl succinic anhydride, iso-octadecyl succinic anhydride and / or 1-octyl-2-decyl succinic anhydride.

In one embodiment of the invention, the at least one alkyl mono-substituted succinic anhydride is selected from the group consisting of butyl succinic anhydride, hexyl succinic anhydride, heptyl succinic anhydride, octyl succinic anhydride, hexadecyl succinic anhydride, Octadecyl succinic anhydride and mixtures thereof.

In one embodiment of the invention, the at least one monosubstituted succinic anhydride is an alkyl monosubstituted succinic anhydride. For example, an alkyl monosubstituted succinic anhydride is butyl succinic anhydride. Alternatively, an alkyl monosubstituted succinic anhydride is hexyl succinic anhydride. Alternatively, an alkyl monosubstituted succinic anhydride is heptyl succinic anhydride or octyl succinic anhydride. Alternatively, an alkyl monosubstituted succinic anhydride is hexadecyl succinic anhydride. For example, an alkyl monosubstituted succinic anhydride is a linear hexadecyl succinic anhydride such as n-hexadecane succinic anhydride; or a branched chain hexadecyl succinic anhydride such as 1-hexyl-2-mercaptosuccinic anhydride. Alternatively, an alkyl monosubstituted succinic anhydride is octadecyl succinic anhydride. For example, an alkyl monosubstituted succinic anhydride is a linear octadecyl succinic anhydride such as n-octadecyl succinic anhydride; or a branched chain octadecyl succinic anhydride such as isooctyl succinic anhydride or 1-octyl- 2-mercaptosuccinic anhydride.

In one embodiment of the invention, an alkyl monosubstituted succinic anhydride is a butyl succinic anhydride such as n-butyl succinic anhydride.

In one embodiment of the invention, the at least one monosubstituted succinic anhydride is a mixture of two or more than two alkyl monosubstituted succinic anhydrides. For example, at least one monosubstituted succinic anhydride is a mixture of two or three alkyl monosubstituted succinic anhydrides.

In one embodiment of the invention, the at least one monosubstituted succinic anhydride consists of a succinic anhydride monosubstituted by a group which is a linear or branched alkenyl group, wherein the group has a C2 to C30 in the substituent, and In the case of a branched chain group, the total amount of carbon atoms of C3 to C30, preferably C3 to C25 and most preferably C4 to C20.

In the meaning of the present invention, the term "alkenyl" means a straight or branched chain unsaturated organic compound composed of carbon and hydrogen. The organic compound further contains at least one double bond, preferably one double bond, in the substituent. In other words, "alkenyl monosubstituted succinic anhydride" is composed of a linear or branched saturated hydrocarbon chain containing a pendant succinic anhydride group. It should be understood that in the meaning of the present invention, the term "alkenyl" includes cis isomers and trans isomers.

In one embodiment of the invention, the at least one monosubstituted succinic anhydride is at least one linear or branched alkenyl monosubstituted succinic anhydride. For example, the at least one alkenyl mono-substituted succinic anhydride is selected from the group consisting of vinyl succinic anhydride, acryl succinic anhydride, butenyl succinic anhydride, triisobutenyl succinic anhydride, pentenyl succinic anhydride, hexene Succinic anhydride, heptenyl succinic anhydride, octenyl succinic anhydride, nonenyl succinic anhydride, decenyl succinic anhydride, dodecenyl succinic anhydride, hexadecenyl succinic anhydride, octadecyl succinic anhydride and mixture.

Thus, it will be appreciated that, for example, the term "hexadecenyl succinic anhydride" encompasses both linear and branched hexadecenyl succinic anhydrides. A specific example of linear heptadecenyl succinic anhydride is n-hexadecenyl succinic anhydride such as 14-hexadecenyl succinic anhydride, 13-hexadecenyl succinic anhydride, 12-hexadecenyl succinic anhydride, 11 -hexadecenyl succinic anhydride, 10-hexadecenyl succinic anhydride, 9-hexadecenyl succinic anhydride, 8-hexadecenyl succinic anhydride, 7-hexadecenyl succinic anhydride, 6-hexadecenyl Succinic anhydride, 5-hexadecenyl succinic anhydride, 4-hexadecenyl succinic anhydride, 3-hexadecenyl succinic anhydride, and/or 2-hexadecenyl succinic anhydride. Specific examples of the branched chain hexadecenyl succinic anhydride are 14-methyl-9-pentadecenyl succinic anhydride, 14-methyl-2-pentadecenyl succinic anhydride, 1-hexyl-2-nonenyl amber Anhydride and/or isohexadecenyl succinic anhydride.

Furthermore, it is to be understood that, for example, the term "octadecenyl succinic anhydride" encompasses both linear and branched octadecyl succinic anhydrides. A specific example of a linear octadecyl succinic anhydride is n-octadecyl succinic anhydride such as 16-octadecenyl succinic anhydride, 15-octadecenyl succinic anhydride, 14-octadecyl succinic anhydride, 13 -octadecyl succinic anhydride, 12-octadecyl succinic anhydride, 11-octadecyl succinic anhydride, 10-octadecyl succinic anhydride, 9-octadecyl succinic anhydride, 8-octadecyl Succinic anhydride, 7-octadecenyl succinic anhydride, 6-octadecyl succinic anhydride, 5-octadecyl succinic anhydride, 4-octadecyl succinic anhydride, 3- octadecyl succinic anhydride and/or 2-octadecyl succinic anhydride. Specific examples of the branched octadecyl succinic anhydride are 16-methyl-9-heptadecenyl succinic anhydride, 16-methyl-7-heptadecenyl succinic anhydride, 1-octyl-2-nonenyl Succinic anhydride and/or isooctadecenyl succinic anhydride.

In one embodiment of the invention, the at least one alkenyl monosubstituted succinic anhydride is selected from the group consisting of hexenyl succinic anhydride, octenyl succinic anhydride, hexadecenyl succinic anhydride, octadecyl succinic anhydride And mixtures thereof.

In one embodiment of the invention, the at least one monosubstituted succinic anhydride is an alkenyl monosubstituted succinic anhydride. For example, an alkenyl monosubstituted succinic anhydride is hexenyl succinic anhydride. Alternatively, an alkenyl monosubstituted succinic anhydride is octenyl succinic anhydride. Alternatively, an alkenyl monosubstituted succinic anhydride is hexadecenyl succinic anhydride. For example, an alkenyl monosubstituted succinic anhydride is a linear hexadecenyl succinic anhydride such as n-hexadecenyl succinic anhydride; or a branched chain hexadecenyl succinic anhydride such as 1-hexyl-2-nonenyl Succinic anhydride. Alternatively, an alkenyl monosubstituted succinic anhydride is octadecyl succinic anhydride. For example, an alkyl monosubstituted succinic anhydride is a linear octadecyl succinic anhydride such as n-octadecyl succinic anhydride; or a branched chain octadecyl succinic anhydride such as isooctadecenyl succinic anhydride or 1 - Octyl-2-nonenyl succinic anhydride.

In one embodiment of the invention, an alkenyl monosubstituted succinic anhydride is a linear octadecyl succinic anhydride such as n-octadecyl succinic anhydride. In another embodiment of the invention, an alkenyl monosubstituted succinic anhydride is a linear octenyl succinic anhydride such as n-octenyl succinic anhydride.

If the at least one monosubstituted succinic anhydride is an alkenyl monosubstituted succinic anhydride, it is understood that an alkenyl monosubstituted succinic anhydride is based on the total weight of the at least one monosubstituted succinic anhydride 95 wt% and preferably 96.5 wt% is present.

In one embodiment of the invention, the at least one monosubstituted succinic anhydride is a mixture of two or more than two alkenyl monosubstituted succinic anhydrides. For example, at least one monosubstituted succinic anhydride is a mixture of two or three alkenyl monosubstituted succinic anhydrides.

If at least one monosubstituted succinic anhydride is a mixture of two or more than two alkenyl monosubstituted succinic anhydrides, one alkenyl monosubstituted succinic anhydride is a linear or branched octadecyl succinic anhydride, and the other various alkenyl groups The monosubstituted succinic anhydride is selected from the group consisting of vinyl succinic anhydride, acryl succinic anhydride, butenyl succinic anhydride, pentenyl succinic anhydride, hexenyl succinic anhydride, heptenyl succinic anhydride, nonenyl succinic anhydride, hexadecene Succinic anhydride and mixtures thereof. For example, at least one monosubstituted succinic anhydride is a mixture of two or more than two alkenyl monosubstituted succinic anhydrides, wherein one alkenyl monosubstituted succinic anhydride is linear octadecyl succinic anhydride, and various other alkenyl groups The monosubstituted succinic anhydride is selected from the group consisting of vinyl succinic anhydride, acryl succinic anhydride, butenyl succinic anhydride, pentenyl succinic anhydride, hexenyl succinic anhydride, heptenyl succinic anhydride, nonenyl succinic anhydride, hexadecene Succinic anhydride and mixtures thereof. Alternatively, the at least one monosubstituted succinic anhydride is a mixture of two or more than two alkenyl monosubstituted succinic anhydrides, wherein one alkenyl monosubstituted succinic anhydride is a branched chain octadecyl succinic anhydride and the other various alkenyl monosubstituted The succinic anhydride is selected from the group consisting of vinyl succinic anhydride, acryl succinic anhydride, butenyl succinic anhydride, pentenyl succinic anhydride, hexenyl succinic anhydride, heptenyl succinic anhydride, nonenyl succinic anhydride, hexadecenyl amber Anhydrides and mixtures thereof.

For example, at least one monosubstituted succinic anhydride is a mixture of two or more alkenyl monosubstituted succinic anhydrides comprising one or more hexadecenyl succinic anhydrides, such as linear or branched hexadecenyl amber An acid anhydride; and one or more octadecyl succinic anhydrides, such as linear or branched octadecyl succinic anhydride.

In one embodiment of the invention, the at least one monosubstituted succinic anhydride is a mixture of two or more than two alkenyl monosubstituted succinic anhydrides comprising linear hexadecenyl succinic anhydride and linear octadecyl amber Anhydride. Alternatively, the at least one monosubstituted succinic anhydride is a mixture of two or more than two alkenyl monosubstituted succinic anhydrides comprising a branched chain hexadecenyl succinic anhydride and a branched chain octadecyl succinic anhydride. For example, the one or more hexadecenyl succinic anhydride is a linear hexadecenyl succinic anhydride such as n-hexadecenyl succinic anhydride; and/or a branched chain hexadecenyl succinic anhydride such as 1-hexyl-2 - nonenyl succinic anhydride. Additionally or alternatively, the one or more octadecyl succinic anhydrides are linear octadecyl succinic anhydrides such as n-octadecyl succinic anhydride; and/or branched octadecyl succinic anhydride, such as Octenyl succinic anhydride and / or 1-octyl-2-nonenyl succinic anhydride.

If the at least one monosubstituted succinic anhydride is a mixture of two or more than two alkenyl monosubstituted succinic anhydrides, an alkenyl monosubstituted succinic anhydride may be from 20% to 60% by weight based on the total weight of the at least one monosubstituted succinic anhydride And preferably present in an amount of from 30% by weight to 50% by weight.

For example, if at least one monosubstituted succinic anhydride is a mixture of two or more alkenyl monosubstituted succinic anhydrides, it comprises one or more hexadecenyl succinic anhydrides, such as linear or branched hexadecyl groups. Succinic anhydride; and one or more octadecyl succinic anhydrides, such as linear or branched hexadecenyl succinic anhydride, one or more octadecyl succinic anhydrides based on the total weight of at least one monosubstituted succinic anhydride It is present in an amount of from 20% by weight to 60% by weight and preferably from 30% by weight to 50% by weight.

It will also be appreciated that the at least one monosubstituted succinic anhydride can be a mixture of at least one alkyl monosubstituted succinic anhydride and at least one alkenyl monosubstituted succinic anhydride.

If at least one monosubstituted succinic anhydride is a mixture of at least one alkyl monosubstituted succinic anhydride and at least one alkenyl monosubstituted succinic anhydride, it is understood that the alkyl substituent in at least one alkyl monosubstituted succinic anhydride and at least one alkene The alkenyl substituent in the mono-substituted succinic anhydride is preferably the same. For example, at least one monosubstituted succinic anhydride is a mixture of ethyl succinic anhydride and vinyl succinic anhydride. Alternatively, the at least one monosubstituted succinic anhydride is a mixture of propyl succinic anhydride and propylene succinic anhydride. Alternatively, the at least one monosubstituted succinic anhydride is a mixture of butyl succinic anhydride and butenyl succinic anhydride. Alternatively, the at least one monosubstituted succinic anhydride is a mixture of triisobutyl succinic anhydride and triisobutenyl succinic anhydride. Alternatively, the at least one monosubstituted succinic anhydride is a mixture of pentyl succinic anhydride and pentenyl succinic anhydride. Alternatively, the at least one monosubstituted succinic anhydride is a mixture of hexyl succinic anhydride and hexenyl succinic anhydride. Alternatively, the at least one monosubstituted succinic anhydride is a mixture of heptyl succinic anhydride and heptenyl succinic anhydride. Alternatively, the at least one monosubstituted succinic anhydride is a mixture of octyl succinic anhydride and octenyl succinic anhydride. Alternatively, the at least one monosubstituted succinic anhydride is a mixture of decyl succinic anhydride and nonenyl succinic anhydride. Alternatively, the at least one monosubstituted succinic anhydride is a mixture of decyl succinic anhydride and nonenyl succinic anhydride. Alternatively, the at least one monosubstituted succinic anhydride is a mixture of dodecyl succinic anhydride and dodecenyl succinic anhydride. Alternatively, the at least one monosubstituted succinic anhydride is a mixture of hexadecyl succinic anhydride and hexadecenyl succinic anhydride. For example, the at least one monosubstituted succinic anhydride is a mixture of linear hexadecanyl succinic anhydride and linear hexadecenyl succinic anhydride, or a mixture of branched chain hexadecanol succinic anhydride and branched chain hexadecenyl succinic anhydride. Alternatively, the at least one monosubstituted succinic anhydride is a mixture of octadecyl succinic anhydride and octadecyl succinic anhydride. For example, the at least one monosubstituted succinic anhydride is a mixture of linear octadecyl succinic anhydride and linear octadecyl succinic anhydride, or a mixture of branched octadecyl succinic anhydride and branched octadecyl succinic anhydride.

In one embodiment of the invention, the at least one monosubstituted succinic anhydride is a mixture of decyl succinic anhydride and nonenyl succinic anhydride.

If the at least one monosubstituted succinic anhydride is a mixture of at least one alkyl monosubstituted succinic anhydride and at least one alkenyl monosubstituted succinic anhydride, the weight between the at least one alkyl monosubstituted succinic anhydride and the at least one alkenyl monosubstituted succinic anhydride The ratio can be between 90:10 and 10:90 (wt%/wt%). For example, the weight ratio between the at least one alkyl monosubstituted succinic anhydride and the at least one alkenyl monosubstituted succinic anhydride can be between 70:30 and 30:70 (wt%/wt%) or 60:40 and 40. : 60 between.

Alkenyl monosubstituted succinic anhydrides are well known to the skilled artisan and are commercially available, for example, from Bercen Corporation, Kemira or Albemarle.

Other known alkenyl monosubstituted succinic anhydrides are branched chain hexadecenyl succinic anhydride (CAS number 32072-96-1), branched chain octadecyl succinic anhydride (CAS number 28777-98-2), and dihydrogen C _15-20 alkenyl 2,5-furandione derivative (2,5-Furandione, dihydro-, mono-C _15-20 -alkenyl derivs). (CAS number 68784-12-3). According to a preferred embodiment of the invention, the at least one monosubstituted succinic anhydride is a dihydromono C _15-20 alkenyl 2,5-furandione derivative. (CAS number 68784-12-3).

Commercially available monosubstituted succinic anhydride solutions may optionally contain other compounds, such as monosubstituted succinic acid.

According to one embodiment of the invention, at least one alkenyl monosubstituted succinic anhydride is used prior to compounding the polymer composition, since at least one monosubstituted succinic anhydride and/or its salty reaction product is present in at least one comprising calcium carbonate On the surface of the material.

According to a preferred embodiment of the invention, at least one monosubstituted succinic anhydride and/or its salt-containing reaction product is present on the surface of at least one material comprising calcium carbonate in the form of a surface treatment layer.

In the meaning of the present invention, the term "surface treatment layer" or "surface treated filler material" means a filler material comprising calcium carbonate which has been treated as a surface treatment. At least one monosubstituted succinic anhydride is contacted to obtain a coating comprising at least one monosubstituted succinic anhydride and/or its salty reaction product on at least a portion of the surface of the calcium carbonate containing filler material. Such surface treated materials comprising calcium carbonate and methods for their preparation are described in WO 2014/060286 A1.

Accordingly, it is to be understood that the treatment layer formed on the surface of at least one filler material comprising calcium carbonate comprises at least one monosubstituted succinic anhydride and/or from at least one filler material comprising calcium carbonate and at least one monosubstituted succinic anhydride Its salt-containing reaction product obtained by contact. The salt-containing reaction product is, for example, one or more calcium salts of at least one monosubstituted succinic anhydride.

Accordingly, it is to be understood that the surface treated filler material comprises or preferably consists of at least one filler material comprising calcium carbonate and a treatment layer comprising at least one monosubstituted succinic anhydride and/or Or its salt-containing reaction product. A treatment layer is formed on the surface of the at least one filler material comprising calcium carbonate.

In one embodiment of the invention, the treatment layer on the surface of at least one filler material comprising calcium carbonate comprises at least one monosubstituted succinic acid, wherein at least one monosubstituted succinic acid is derived from at least one monosubstituted succinic anhydride applied form.

In one embodiment of the invention, the treatment layer formed on the surface of at least one filler material comprising calcium carbonate comprises at least one monosubstituted succinic anhydride, and at least one monosubstituted succinic acid or from at least one comprising calcium carbonate. A salt-containing reaction product obtained by contacting a filler material with at least one monosubstituted succinic anhydride and optionally at least one monosubstituted succinic acid. Alternatively, the treatment layer formed on the surface of at least one filler material comprising calcium carbonate comprises at least one monosubstituted succinic anhydride, and at least one monosubstituted succinic acid and at least one filler material comprising at least one calcium carbonate and at least one single a salt-containing reaction product obtained by contacting succinic anhydride and optionally at least one monosubstituted succinic acid.

Preferably, the treatment layer is characterized in that the total weight of the at least one monosubstituted succinic anhydride and the at least one monosubstituted succinic acid and/or its salt-containing reaction product on the surface of the surface treated filler material is at least one comprising calcium carbonate. The filler material is from 0.1 mg per square meter to 5 mg per square meter, more preferably from 0.2 mg per square meter to 4 mg per square meter and most preferably from 1 mg per square meter to 4 mg per square meter.

Preferably, the treatment layer is characterized in that the total weight of the at least one monosubstituted succinic anhydride and the at least one monosubstituted succinic acid and/or its salt-containing reaction product on the surface of the surface treated filler material is at least one comprising calcium carbonate. The filler material is 0.05 wt% per square meter to 1 wt% per square meter, more preferably 0.1 wt% per square meter to 0.5 wt% per square meter and optimally 0.15 wt% per square meter to per square meter Ruler 0.25wt%.

Additionally or alternatively, the treated layer of the surface treated filler material product comprises at least one monosubstituted succinic anhydride and at least one monosubstituted succinic acid and/or its salt containing reaction product in a particular molar ratio. For example, the molar ratio of the at least one monosubstituted succinic anhydride and the at least one monosubstituted succinic acid to its salty reaction product is from 99.9:0.1 to 0.1:99.9, preferably from 70:30 to 90:10.

In the meaning of the present invention, "molar ratio of the at least one mono-substituted succinic anhydride and the at least one mono- The term "substituted succinic acid to the salty reaction product(s)thereof"" refers to the sum of the molecular weights of at least one monosubstituted succinic anhydride and the sum of the molecular weights of at least one monosubstituted succinic acid compared to the monosubstituted amber in the salty reaction product thereof. The sum of the molecular weights of the anhydride molecules and the sum of the molecular weights of the monosubstituted succinic acid molecules in the salt-containing reaction product.

It will be further appreciated that the surface treated filler material obtained comprises from 0.1 wt% to 4.0 wt%, preferably from 0.1 wt% to 2.5, based on the total dry weight of at least one filler material comprising calcium carbonate. The amount of wt%, more preferably from 0.1 wt% to 2 wt%, even more preferably from 0.1 wt% to 1.5 wt%, even more preferably from 0.1 wt% to 1 wt% and most preferably 0.2 wt% A treatment layer in an amount of 0.8% by weight.

In view of the excellent results obtained, in accordance with a preferred embodiment of the present invention, the surface treated filler material comprises a) at least one filler material comprising calcium carbonate having i) in the range of from 0.1 μm to 10 μm Weight median particle size d ₅₀ value, and / or ii) Top cut of 15μm (d _98), and / or iii) in accordance with ISO 9277: 2010 using nitrogen and the BET method of measuring, 0.5m ² / g to 150m ² / g of specific surface area (BET), and / or iv a residual total water content of from 0.01 wt% to 1 wt%, based on the total dry weight of at least one filler material comprising calcium carbonate, and b) a treatment layer on the surface of at least one filler material comprising calcium carbonate, It comprises at least one monosubstituted succinic anhydride and at least one monosubstituted succinic acid and/or its salt-containing reaction product.

According to another preferred embodiment of the invention, the surface treated filler material comprises a) at least one filler material comprising calcium carbonate having i) a weight median particle size d _{50 in the} range from 0.1 μm to 10 μm Value, and / or ii) Top cut of 15μm (d _98), and / or iii) in accordance with ISO 9277: 2010 using nitrogen and the BET method of measuring, 0.5m ² / g to 150m ² / g of specific surface area (BET), and / or iv a residual total water content of from 0.01 wt% to 1 wt%, based on the total dry weight of at least one filler material comprising calcium carbonate, and b) a treatment layer on the surface of at least one filler material comprising calcium carbonate, Including at least one monosubstituted succinic anhydride and at least one monosubstituted succinic acid and/or its salt-containing reaction product

The surface treated filler material comprises a treatment layer in an amount of from 0.1% by weight to 3% by weight based on the total dry weight of the at least one calcium carbonate-containing filler material.

According to another embodiment of the present invention, at least one monosubstituted succinic anhydride is used during compounding of the polymer composition because at least one monosubstituted succinic anhydride is mixed with polylactic acid as a polymer component and at least one comprises carbonic acid. The calcium material is contacted as a polymer composition of the filler. Thus, at least one monosubstituted succinic anhydride is not present on the surface of the filler material comprising calcium carbonate prior to mixing and/or compounding. However, during the compounding step, at least some of the monosubstituted succinic anhydrides may be on the surface of the filler material comprising calcium carbonate. Thus, after compounding the monosubstituted succinic anhydride, the polymer composition comprises polylactic acid (as a polymer component), at least one material comprising calcium carbonate (as a filler), wherein a portion of the filler material comprising calcium carbonate comprises A treatment layer on the surface of at least one filler material comprising calcium carbonate comprising at least one monosubstituted succinic anhydride and at least one monosubstituted succinic acid and/or its salt-containing reaction product.

According to another embodiment of the invention, the at least one monosubstituted succinic anhydride and/or its salt-containing reaction product is present in an amount of at least 0.1% by weight, based on the total dry weight of at least one filler material comprising calcium carbonate, preferably An amount of from 0.1 wt% to 4.0 wt%, more preferably from 0.1 wt% to 3.0 wt%, even more preferably from 0.2 wt% to 2.0 wt%, even more preferably from 0.3 wt% to 1.5 wt% And it is preferably present in the polymer composition in an amount of from 0.4% by weight to 1.2% by weight.

According to another embodiment of the invention, the at least one monosubstituted succinic anhydride and/or its salt-containing reaction product is present in an amount of at least 0.005 wt%, preferably from 0.01 wt% to 5.0 wt%, based on the total weight of the polymer component The amount of %, more preferably from 0.02 wt% to 1.0 wt%, even more preferably from 0.03 wt% to 0.8 wt%, even more preferably from 0.05 wt% to 0.5 wt% and most preferably from 0.07 wt% An amount of from % to 0.3% by weight is present in the polymer composition.

The present inventors have surprisingly found that by using at least one monosubstituted succinic anhydride before or during compounding of the polymer composition as described above, polylactic acid is included as a polymer component and a material comprising calcium carbonate as a filler. The stability, especially the thermal stability, of the polymer composition can be improved. Therefore, the decomposition of the polymer during processing is reduced. Additionally or alternatively, the processability of such polymer compositions can be promoted. The mechanical properties of such polymer compositions, especially the melt flow rate, can also be improved.

More precisely, the inventors have surprisingly found that by using at least one monosubstituted succinic anhydride before or during the compounding of the polymer composition as described above, according to DIN EN ISO 1133-1:2011 (Procedure A, 2.16 kg, 210 ° C, granules), measured by the melt flow rate of such compounded polymer compositions compared to the same polymer composition that has been treated in the same manner in the absence of at least one monosubstituted succinic anhydride Reduce by at least 10%.

According to the invention, the term "the same polymer composition that has been treated the same way without at least one mono-substituted" "Succinic anhydride"" means a comparative polymer composition that does not contain a monosubstituted succinic anhydride. Apart from this, the polymer composition according to the invention is identical to the comparative polymer composition, which means that both comprise the same compound. Moreover, these two polymer compositions have been treated in the same manner, which means that the compounding and storage processes are the same.

According to an embodiment of the present invention, at least one monosubstituted succinic anhydride is used during or during the compounding before or during the compounding of the polymer composition comprising polylactic acid as the polymer component and at least one material comprising calcium carbonate as the filler. Reduction of polymer decomposition and/or measurement according to DIN EN ISO 1133-1:2011 (procedure A, 2, 16 kg, 210 ° C, granules) in the same manner as in the absence of at least one monosubstituted succinic anhydride The melt flow rate of such compounded polymer compositions is reduced by at least 10%, preferably by at least 15%, more preferably by at least 20%, and most preferably by at least 25%, compared to the composition.

According to another embodiment of the present invention, at least one monosubstituted succinic anhydride is used before or during compounding a polymer composition comprising polylactic acid as a polymer component and at least one material comprising calcium carbonate as a filler, according to DIN EN ISO 1133-1:2011 (Procedure A, 2, 16 kg, 210 ° C, granules), as compared to the same polymer composition which has been treated in the same manner in the absence of at least one monosubstituted succinic anhydride The melted flow rate of the compounded polymer composition is reduced by at least 10%, preferably by at least 15%, more preferably by at least 20% and optimally by at least 25%.

According to another embodiment of the present invention, by compounding a polymer composition consisting of polylactic acid (as a polymer component), other polymer components, and at least one material comprising calcium carbonate (as a filler) Or during the use of at least one monosubstituted succinic anhydride, measured according to DIN EN ISO 1133-1:2011 (procedure A, 2, 16 kg, 210 ° C, granules), in the same manner as in the absence of at least one monosubstituted succinic anhydride The melt flow rate of such compounded polymer compositions is reduced by at least 10%, preferably by at least 15%, more preferably by at least 20%, and most preferably by at least 25%, compared to the same polymer composition.

According to another embodiment of the present invention, at least one single is used before or during compounding a polymer composition composed of polylactic acid (as a polymer component) and at least one material comprising calcium carbonate (as a filler) Substituted succinic anhydride, as measured according to DIN EN ISO 1133-1:2011 (procedure A, 2, 16 kg, 210 ° C, granules), identical polymer composition treated in the same manner as at least one monosubstituted succinic anhydride In contrast, such compounded polymer compositions have a melt flow rate that is reduced by at least 10%, preferably by at least 15%, more preferably by at least 20%, and most preferably by at least 25%.

According to another embodiment of the present invention, at least one monosubstituted amber is used during compounding of a polymer composition consisting of polylactic acid (as a polymer component) and at least one material comprising calcium carbonate (as a filler) Anhydride, as measured according to DIN EN ISO 1133-1:2011 (Procedure A, 2, 16 kg, 210 ° C, granules), compared to the same polymer composition which has been treated in the same manner in the absence of at least one monosubstituted succinic anhydride The melt flow rate of such a compounded polymer composition is reduced by at least 10%, preferably at least 15%, more preferably at least 20% and most preferably at least 25%, wherein at least one monosubstituted succinic anhydride and/or The salt-containing reaction product is present on the surface of at least one material comprising calcium carbonate.

According to another embodiment of the invention, the tensile strain at break of the polymer composition is increased by at least 40%, preferably at least 100%, more preferably at least 200, compared to the same polymer composition lacking at least one monosubstituted succinic anhydride. % and best at least 300%.

Method for reducing polymer decomposition and/or reducing melt flow rate during processing

The invention further comprises a method according to claim 1 for reducing the decomposition of the polymer during processing and/or reducing the melt flow rate of the polymer composition. More specifically, the polymer composition comprises polylactic acid as a polymer component and at least one material comprising calcium carbonate as a filler. By the method according to the invention, according to DIN EN ISO 1133-1:2011 (procedure A, 2, 16 kg, 210 ° C, granules), the same polymer composition which has been treated in the same manner in the absence of at least one monosubstituted succinic anhydride The melt flow rate can be reduced by at least 10% compared to the material. The method comprises the steps of: a) providing at least one polylactic acid as a polymer component, and b) providing at least one material comprising calcium carbonate as a filler, and c) providing at least one monosubstituted succinic anhydride, and d) causing a The components of b) and c) are contacted in any order, and e) the contact components of step d) are compounded.

According to a specific embodiment of the invention, there is provided a method for reducing polymer decomposition during processing and/or measuring according to DIN EN ISO 1133-1:2011 (procedures A, 2, 16 kg, 210 ° C, particles), and at least Melt flow rate of a polymer composition comprising polylactic acid as a polymer component and at least one material comprising calcium carbonate as a filler, compared to the same polymer composition of monosubstituted succinic anhydride which has been treated in the same manner A method of reducing at least 10%, the method comprising: a) providing at least one polylactic acid as a polymer component, and b) providing at least one material comprising calcium carbonate as a filler, and c) providing at least one monosubstituted succinic anhydride d) The components of a), b) and c) are contacted in any order, and e) the contact components of step d) are compounded.

According to step a), at least one polylactic acid is provided as a polymer component as defined above. The polylactic acid may be provided in a solid form or in a molten form.

According to the invention, the term "solid" means a material which is solid at standard ambient temperature and pressure (SATP), which means a temperature of 298.15 K (25 ° C) and exactly 100000 Pa (1 bar, 14.5). Absolute pressure of psi, 0.98692atm). The solid can be in the form of a powder, a lozenge, a granule, a flake or the like.

In accordance with the present invention, the term "ambient pressure" means standard ambient temperature pressure (SATP), which refers to an absolute pressure of exactly 100 000 Pa (1 bar, 14.5 psi, 0.98692 atm).

According to the invention, the term "molten" means a material that melts or viscous at standard ambient temperature and pressure (SATP), which means a temperature of 298.15 K (25 ° C) and exactly 100000 Pa (1 bar). Absolute pressure of 14.5 psi, 0.98692 atm).

According to a preferred embodiment of the invention, at least one polylactic acid may be provided in solid form and preferably in the form of granules or pellets.

According to another embodiment of the invention, other polymer components are provided in addition to polylactic acid. The other polymer component can be, for example, a polyester as defined above. According to a preferred embodiment of the invention, only polylactic acid is provided as a polymer component.

According to step b), at least one filler material comprising calcium carbonate is provided as defined above. The material comprising calcium carbonate can be provided in dry form.

The term "dry/dried" material is understood to mean a material having between 0.001 wt% and 0.5 wt% water, based on the total weight of the material comprising calcium carbonate.

According to a specific example of the present invention, the amount is from 0.1% by weight to 85% by weight, preferably from 3% by weight to 50% by weight, more preferably from 5% by weight to 40% by weight, based on the total weight of the polymer component. And the material containing calcium carbonate is preferably supplied in an amount of 10% by weight to 30% by weight.

According to step c), at least one monosubstituted succinic anhydride is provided as defined above.

According to a specific embodiment of the present invention, the total dry weight of the at least one filler material comprising calcium carbonate is preferably at least 0.1 wt%, preferably from 0.1 wt% to 4.0 wt%, more preferably An amount of from 0.1 wt% to 3.0 wt%, even more preferably from 0.2 wt% to 2.0 wt%, even more preferably from 0.3 wt% to 1.5 wt%, and most preferably from 0.4 wt% to 1.2 wt% At least one monosubstituted succinic anhydride is provided.

According to a specific embodiment of the present invention, the amount is at least 0.005 wt%, preferably 0.01 wt% to 5.0 wt%, more preferably 0.02 wt% to 1.0 wt%, based on the total weight of the polymer component. An amount, even more preferably, of at least one monosubstituted succinic anhydride is provided in an amount of from 0.03 wt% to 0.8 wt%, even more preferably from 0.05 wt% to 0.5 wt%, and optimally from 0.07 wt% to 0.3 wt%. .

At least one monosubstituted succinic anhydride will be provided in solid form or in liquid form. According to a preferred embodiment, at least one monosubstituted succinic anhydride is provided in liquid form.

Liquid monosubstituted succinic anhydride according to the invention means when measured at a shear rate of 5 s ^-1 and at +20 ° C (± 2 ° C) using suitable equipment, for example equipped with measuring units TEZ 150 PC and CC 28.7 When measuring the Physica MCR 300 rheometer (Paar Physica), the viscosity is below 5000 mPa at +20 °C (±2 °C). s, preferably less than 2500 mPa. s, better than 1000mPa. s and the best is less than 500mPa. s material.

If at least one monosubstituted succinic anhydride is used to form a surface layer on the surface of at least one material comprising calcium carbonate, at least one monosubstituted succinic anhydride will be provided in an amount such that it is in at least one filler material comprising calcium carbonate. The total weight of the at least one monosubstituted succinic anhydride and/or its salt-containing reaction product on the surface is at least one filler material comprising calcium carbonate of less than 5 mg per square meter, preferably less than 4.5 mg per square meter and The optimum is less than 4.0 mg per square meter. For example, it is preferred to provide at least one monosubstituted succinic anhydride in an amount such that the total weight of the at least one monosubstituted succinic anhydride and/or its salt-containing reaction product is at least one calcium carbonate-containing filler material per square metric It is from 0.1 mg to 5 mg per square meter, more preferably from 0.2 mg per square meter to 4 mg per square meter and most preferably from 1 mg per square meter to 4 mg per square meter.

According to step d), the components of a), b) and c) are brought into contact in any order.

The contacting of step d) can be carried out under mixing conditions.

The skilled person will adjust the mixing conditions (such as the configuration of mixing time and mixing speed) according to their method equipment.

For example, mixing and homogenization can be carried out by means of a ploughshare mixer. The ploughshare mixer operates by a mechanically constructed fluidized bed principle. The ploughshare blade rotates near the inner wall of the horizontal cylindrical drum and conveys the mixture components from the product bed to the open mixing space. The mechanically manufactured fluidized bed ensures even strong mixing of large batches of material in a very short time. A chopper and/or a disperser is used to disperse the agglomerates in the drying operation. Equipment that can be used in the process of the invention is commercially available, for example, from Gebrüder Lödige Maschinenbau, Germany.

According to another embodiment of the invention, method step d) can be carried out in a grinding apparatus, such as in a ball mill, a hammer mill, a rod mill, a vibratory mill, a roller mill, a centrifugal impact mill, a vertical bead mill, Performed in a grinder, a pin mill or a hammer mill.

Process step d) can be carried out at a temperature between 15 ° C and 150 ° C and preferably at room temperature, that is to say at a temperature of 20 ° C ± 2 ° C. According to a particular embodiment of the invention, process step d) is carried out for at least 1 s, preferably at least 1 min, for example at least 15 min, 30 min, 1 hour, 2 hours, 4 hours, 6 hours, 8 hours or 10 hours.

According to a specific example, step d) comprises the steps of: i) mixing the polymer component of step a) with the filler material of step b), and ii) reacting the monosubstituted succinic anhydride of step c) with step i) The mixture is mixed.

According to another embodiment, step d) comprises the steps of: i) combining the polymer component of step a) with the monosubstituted succinic anhydride of step c), and ii) the filler material of step b) with step i) The mixture is mixed.

According to another embodiment, step d) comprises simultaneously mixing the polymer component of step a), the monosubstituted succinic anhydride of step c) and the filler material of step b) in one step.

According to another embodiment, step d) comprises the steps of: i) partially mixing the polymer component of step a) with one of the monosubstituted succinic anhydrides of step c), ii) the filler material of step b) and step c The remainder of the monosubstituted succinic anhydride is mixed, and iii) the step i) is combined with the composition of step ii). The monosubstituted succinic anhydride mixed with the polymeric component and the monosubstituted succinic anhydride mixed with the filler material can be the same monosubstituted succinic anhydride or can be different monosubstituted succinic anhydrides. According to a preferred embodiment, the monosubstituted succinic anhydrides are the same.

According to a preferred embodiment, step d) comprises the steps of: i) mixing the filler material of step b) with the monosubstituted succinic anhydride of step c), and ii) polymerizing step a) with step i) The mixture is mixed. More precisely, in the contacting step d), the at least one material comprising calcium carbonate of step b) is first contacted with at least one monosubstituted succinic anhydride of step c) in one or more steps with mixing, such that a treatment layer comprising at least one monosubstituted succinic anhydride and/or a salt-containing reaction product thereof is formed on the surface of the at least one material comprising calcium carbonate of step b), and secondarily, the surface treated calcium carbonate is mixed under mixing The material is contacted with polylactic acid in one or more steps.

According to another preferred embodiment, step d) comprises the steps of: i) partially mixing the filler material of step b) with one of the monosubstituted succinic anhydrides of step c), and ii) polymerizing the polymer component of step a) And the remainder of the monosubstituted succinic anhydride is mixed with the mixture of step i). More specifically, in the contacting step d), the at least one material comprising calcium carbonate of step b) is first contacted with one of the at least one monosubstituted succinic anhydride of step c) in one or more steps, under mixing, Forming a treatment layer comprising at least one monosubstituted succinic anhydride and/or its salt-containing reaction product on the surface of the at least one calcium carbonate-containing material of step b), and secondarily subjecting the surface treated to inclusion under mixing The calcium carbonate material is contacted with the remainder of the polylactic acid and the monosubstituted succinic anhydride in one or more steps. The monosubstituted succinic anhydride mixed with the polymeric component and the monosubstituted succinic anhydride mixed with the filler material can be the same monosubstituted succinic anhydride or can be different monosubstituted succinic anhydrides. According to a preferred embodiment, the monosubstituted succinic anhydrides are different succinic anhydrides.

If, in the contacting step d), at least one material comprising calcium carbonate of step b) is first contacted with at least one monosubstituted succinic anhydride or a portion thereof of step c) in one or more steps, such that it comprises The treatment layer of at least one monosubstituted succinic anhydride and/or its salt-containing reaction product is formed on the surface of the at least one material comprising calcium carbonate of step b), and the contacting can be carried out as follows.

Contact of at least one filler material comprising calcium carbonate with at least one monosubstituted succinic anhydride can be carried out under mixing conditions. The skilled person will adjust these mixing conditions (such as the configuration of mixing time and mixing speed) according to their method equipment.

In a preferred embodiment of the invention, the contacting of at least one filler material comprising calcium carbonate with at least one monosubstituted succinic anhydride can be a continuous process. In this case, at least one filler material comprising calcium carbonate can be contacted with at least one monosubstituted succinic anhydride in a constant stream form such that a constant concentration of at least one monosubstituted succinic anhydride is provided.

Alternatively, at least one filler material comprising calcium carbonate is contacted with at least one monosubstituted succinic anhydride in one step, wherein the at least one monosubstituted succinic anhydride is preferably added in one portion.

In another embodiment of the invention, the contacting of at least one filler material comprising calcium carbonate with at least one monosubstituted succinic anhydride can be a batch process, even if at least one calcium carbonate-containing filler material is in more than one step Contacting with at least one monosubstituted succinic anhydride, wherein at least one monosubstituted succinic anhydride is preferably added in about an aliquot. Alternatively, at least one monosubstituted succinic anhydride may be added to at least one calcium carbonate-containing filler material in unequal form, i.e., in larger and smaller portions.

According to one embodiment of the invention, the at least one filler material comprising calcium carbonate is contacted with at least one monosubstituted succinic anhydride in a batch or continuous process for a period of from 0.1 s to 5000 s. For example, the contact of at least one filler material comprising calcium carbonate with at least one monosubstituted succinic anhydride is a continuous process and comprises one or several contacting steps, and the total contact time is from 0.1 s to 4000 s, preferably from 0.5 s to 3000 s. And the best 1s to 2000s.

When at least one monosubstituted succinic anhydride is employed, it can be characterized by a suitable viscosity at about room temperature, i.e., at least one monosubstituted succinic anhydride can be in a liquid state. It is therefore a requirement of the present invention to adjust the temperature during contact of at least one filler material comprising calcium carbonate with at least one monosubstituted succinic anhydride such that at least one monosubstituted succinic anhydride is melted.

Accordingly, it is understood that the temperature is adjusted prior to and/or during the contacting of at least one filler material comprising calcium carbonate with at least one monosubstituted succinic anhydride such that the temperature is at least 2 ° C above the melting point of the at least one monosubstituted succinic anhydride. For example, the temperature is adjusted prior to contacting at least one filler material comprising calcium carbonate with at least one monosubstituted succinic anhydride such that the temperature is at least 2 ° C above the melting point of the at least one monosubstituted succinic anhydride.

In one embodiment of the invention, the temperature is adjusted before and/or during the contacting of at least one filler material comprising calcium carbonate with at least one monosubstituted succinic anhydride such that the temperature is above the melting point of the at least one monosubstituted succinic anhydride It is at least 5 ° C, preferably at least 8 ° C and most preferably at least 10 ° C. For example, the temperature is adjusted before and/or during the contacting of at least one filler material comprising calcium carbonate with at least one monosubstituted succinic anhydride such that the temperature is above 2 ° C to 50 ° C of the melting point of the at least one monosubstituted succinic anhydride Preferably, it is 5 ° C to 40 ° C, more preferably 8 ° C to 30 ° C and most preferably 10 ° C to 20 ° C.

In one embodiment of the invention, the contacting of at least one filler material comprising calcium carbonate with at least one monosubstituted succinic anhydride is thereby carried out at a processing temperature of less than 200 °C. For example, contacting of at least one filler material comprising calcium carbonate with at least one monosubstituted succinic anhydride is carried out at a treatment temperature of from 30 ° C to 200 ° C, preferably from 80 ° C to 150 ° C and optimally from 110 ° C to 130 ° C.

The treatment time for contacting at least one filler material comprising calcium carbonate with at least one monosubstituted succinic anhydride is carried out for a period of 5000 s or less, preferably 4000 s or less, more preferably 3000 s or less than 3000 s And the best 0.1s to 2000s. For example, contact of at least one filler material comprising calcium carbonate with at least one monosubstituted succinic anhydride is carried out for a period of 1200 s. Generally, the duration of the contact is determined by the processing temperature applied during contact of at least one filler material comprising calcium carbonate with at least one monosubstituted succinic anhydride. For example, in the case of applying a treatment temperature of about 200 ° C, the treatment time is as short as, for example, about 0.1 s. If a treatment temperature of about 120 ° C is applied, the treatment time can be as long as, for example, about 1200 s.

In one embodiment of the invention, at least one filler material comprising calcium carbonate is preheated, i.e., activated, prior to contacting at least one filler material comprising calcium carbonate with at least one monosubstituted succinic anhydride. In other words, before at least one filler material comprising calcium carbonate is contacted with at least one monosubstituted succinic anhydride, at 50 ° C to 200 ° C, preferably 80 ° C to 200 ° C, more preferably 90 ° C to 150 ° C and most preferably 100 ° C At least one filler material comprising calcium carbonate is treated to a temperature of 130 °C. The treatment time for preheating at least one filler material comprising calcium carbonate is carried out for a period of 30 minutes or less, preferably 20 minutes or less, and more preferably 15 minutes or less. In one embodiment of the invention, the at least one calcium carbonate-containing filler material is preheated at a temperature approximately equal to the temperature at which the at least one filler material comprising calcium carbonate is contacted with the at least one monosubstituted succinic anhydride. .

In the meaning of the present invention, the term "equal" means that the temperature is lower than or higher than the temperature at which at least one filler material comprising calcium carbonate is contacted with at least one monosubstituted succinic anhydride, preferably at most 20 ° C, preferably A preheating temperature of at most 15 ° C, more preferably 10 ° C and optimally at most 5 ° C.

According to step e), the contacting components of step d) are compounded. According to the invention, the term "compounding" refers to the preparation of a polymer or plastic formulation. During compounding, the contact components of step d) are mixed and/or blended in a molten or softened state to achieve a homogeneous blend of different materials. The compounding method is known to the skilled person.

According to one embodiment of the invention, compounding and homogenization can be carried out by means of a dough mixer. The dough mixer is capable of mixing and kneading the composition, and in particular having a composition of high viscosity. The kneading machine operates by horizontally rotating the groove or one or more of the delta or Z-shaped blades in the pan. Equipment that can be used can be purchased, for example, from Kenwood Co., Ltd.

According to another embodiment of the invention, compounding and homogenization can be carried out by means of an extruder, such as a single screw extruder or a twin screw extruder. The extruder is capable of mixing and compounding the composition. The extruder operates by rotating one or more screws within the housing. The equipment that can be used can include a base unit and an extruder. For example, the base unit can be Haake Polylab OS from Thermo Scientific and the extruder can be the Rheomex CTW 100 OS from Thermo Scientific.

According to another embodiment of the invention, compounding and homogenization can be carried out by means of a laboratory mixer. The laboratory mixer is capable of mixing and kneading the composition. Equipment that can be used can include a base unit, a blender, and a kneader. For example, the base unit can be a Haake Polylab OS, the blender can be a Haake Rheomix 600 OS, and the kneader can be a Roller Roters 600, all from Thermo Scientific. RheoDrive7 can be used as a software for evaluating test results.

According to another embodiment of the invention, compounding and homogenization can be carried out by means of a two-roll mill. The two-roll mill is capable of mixing and kneading the composition. An exemplary roller mill is the Walzwerk 150x400 from Dr. Collin, Germany.

Process step e) can be carried out at a temperature between 15 ° C and 150 ° C and preferably at room temperature, that is to say at a temperature of 20 ° C ± 2 ° C. According to a particular embodiment of the invention, process step e) is carried out for at least 1 s, preferably at least 1 min, for example at least 15 min, 30 min, 1 hour, 2 hours, 4 hours, 6 hours, 8 hours or 10 hours.

According to another embodiment, heat and pressure can be applied in step e). Heat and pressure can be applied in sequence. In a preferred embodiment, heat and pressure are applied simultaneously. In another preferred embodiment, the heat and/or pressure of the different steps are applied in sequence.

For example, heat and pressure conditions can be applied by means of a hot pressing procedure. For hot pressing, any pressure device can be used which can be additionally heated during the pressing process. Heating can be carried out, for example, by induction heating or by indirect resistance heating. During hot pressing, the mold plate can be cooled by water cooling to control the mold temperature. Equipment that can be used can be purchased, for example, from Dr. Collin, Germany.

It can be carried out at a temperature between 15 ° C and 220 ° C, preferably between 50 ° C and 220 ° C, more preferably between 70 ° C and 220 ° C and optimally at 210 ° C. Hot pressing. It can be at a pressure between 2 and 400 bar, preferably between 10 and 350 bar, more preferably between 15 and 300 bar and most preferably between 15 and 250 bar. Hot pressing under pressure.

According to a specific embodiment of the invention, the hot pressing is carried out for at least 1 s, preferably at least 50 s or at least 100 s, 120 s, 160 s, 180 s, 200 s or 240 s.

The inventors have surprisingly found that the stability, especially the thermal stability, of a polymer composition comprising polylactic acid as a polymer component and a material comprising calcium carbonate as a filler can be improved by the method according to the invention. Thus, the decomposition of the polymer during processing of such polymer compositions is reduced. Additionally or alternatively, the processability of such polymer compositions can be promoted. Additionally or alternatively, the mechanical properties of such polymer compositions, such as melt flow rate, can be improved by the process according to the invention.

More precisely, the inventors have surprisingly found that by means of the process according to the invention, the decomposition of the polymer during processing is reduced and/or according to DIN EN ISO 1133-1:2011 (procedure A, 2.16 kg, 210 ° C, granules) Measured, polymer composition comprising polylactic acid as a polymer component and at least one filler material comprising calcium carbonate, compared to the same polymer composition that has been treated in the same manner lacking at least one monosubstituted succinic anhydride The melt flow rate is reduced by at least 10%, preferably by at least 15%, more preferably by at least 20% and optimally by at least 25%.

According to another embodiment of the invention, by the method according to the invention, polylactic acid is included as a polymer component and at least one filler comprising calcium carbonate is compared to the same polymer composition lacking at least one monosubstituted succinic anhydride The tensile strain of the polymer composition of the agent material is increased by at least 40%, preferably at least 100%, more preferably at least 200% and most preferably at least 300%.

Article according to the invention

Another aspect of the invention relates to an article comprising a polymer composition obtainable by a process comprising the steps of: a) providing at least one polylactic acid as a polymer component, and b) providing at least one comprising carbonic acid a calcium material as a filler, and c) providing at least one monosubstituted succinic anhydride d) contacting the components of a), b) and c) in any order, and e) compounding the contacting component of step d), wherein Products are selected from the group consisting of hygiene products, pharmaceutical and health products, filter products, geotextile products, agricultural and horticultural products, clothing, footwear and luggage products, household and industrial products, packaging products, construction products and Similar.

According to steps a) to c), at least one polylactic acid is provided as a polymer component, at least one material comprising calcium carbonate as a filler and at least one monosubstituted succinic anhydride as defined above.

According to step d) and step e), the components of a), b) and c) are contacted in any order as defined above and the contacting component of step d) is compounded.

Products are selected from the group consisting of hygiene products, pharmaceutical and health products, filter products, geotextile products, agricultural and horticultural products, clothing, footwear and luggage products, household and industrial products, packaging products, construction products and Similar.

Preferably, the hygiene product is selected from the group consisting of absorbent hygiene products such as baby diapers or diapers, feminine hygiene products, adult incontinence products, depilatory strips, bandages and wound dressings, disposable bath towels And face towel, disposable slippers and footwear, top sheet or cover, consumer mask, leg cuff, acquisition/distribution layer, core wrap, back sheet, stretch Stretch ear, positioning area, dusting layer and fastening system; and wipes, such as wet wipes, skin care wipes, baby wipes, facial wipes, cleaning wipes, hand wipes and body wipes Cloth, wet wipes, personal hygiene wipes, feminine hygiene wipes, anti-bacterial wipes and medicinal wipes.

Preferably, the medical and health care products are selected from the group consisting of sterilizable medical products, medical packaging, caps (such as disposable surgical caps), protective clothing, surgical gowns, surgical masks and masks, surgical scrubs, Surgical drape, surgical drape, wrap, packaging, sponge, dressing, swab, bed fabric, pollution control suit, test suit, lab coat, isolation suit, transdermal drug delivery, care Cover, bottom pad, program package, heat pack, ostomy bag liner, strap, incubator mattress, bactericidal wrap (CSR wrap), wound care, cold/hot wrap, drug delivery system ( Such as patch).

Preferably, the filter product is selected from the group consisting of: a gasoline filter, an oil filter, an air filter, a water filter, a coffee filter, a tea bag, a pharmaceutical industry filter, a mineral processing filter, a liquid Cartridges and bag filters, vacuum bags, allergen diaphragms and laminates with non-woven layers.

Preferably, the geotextile product is selected from the group consisting of soil stabilizers and road linings, foundation stabilizers, erosion control members, ditch construction, drainage systems, geomembrane protection members, frozen protection members, agricultural coverings , water barriers for pools and ditches, gravel infiltration barriers for drainage tiles and landfill liners.

Preferably, the agricultural and horticultural products are selected from the group consisting of crop cover, plant protection, seed coating, weed control fabric, greenhouse shelter, root control bag, biodegradable plant pot, capillary pad And landscape fabrics.

Preferably, the clothing, footwear and luggage products are selected from the group consisting of: interlayers (such as front placket, collar, inner gusset, waistband, lower collar, etc.), disposable underwear, shoe components (such as lace eyelets) Reinforcement, sports shoes and sandals reinforcements and insole bushings, bag components, adhesives, compositions and (washing) care labels.

Preferably, the packaged product is selected from the group consisting of: an interlayer, such as a desiccant package, an adsorbent package, a gift box, a document box, a non-woven bag, a book cover, a postal package, a express package, a close-pack, and the like. By.

Preferably, the household and industrial products are selected from the group consisting of abrasives, bed fabrics (such as bagged fabrics for pocket springs, separation layers, spring covers, top covers, bottomed fabrics, duvet covers, pillowcases) Etc.), blinds/curtains, carpet/carpet base fabrics (eg scatter rug, carpet tiles, bath mats, etc.), covering and separating materials, detergent pouches, fabric softener sheets, flooring, furniture/ Interior decoration (such as lining, reverse fabric for padding, dust cover, spring cover, brace, etc.), mop, table cloth, tea bag and coffee bag, vacuum cleaning bag, wall covering, wipe ( Such as household care wipes, floor care wipes, cleaning wipes, pet care wipes, etc., automotive construction, cable coverings, civil engineering, filter packaging, protective clothing, foundation and second layer carpet backing, composite Materials, ship navigation products, tablecloth products, chopped strand mats, base fabrics/stabilizers for machine embroidery, encapsulations requiring air holes, insulation materials (eg fiberglass batt, pillows, cushions) ), litter (such as interior upholstery),褥 or cover covered with cotton wadding, consumer and medical masks, postal envelopes, tarpaulins, tent fabrics and transport (wood, steel) coverings, disposable clothing (such as socks and gowns) and weather-resistant housing Things.

Preferably, the building product is selected from the group consisting of house coverings, asphalt coatings, road and railway subgrades, golf and tennis courts, wall coverings, soundproof wall coverings, roofing materials and tile linings. Pads, soil stabilizers and road liners, foundation stabilizers, erosion control parts, ditch construction, drainage systems, geomembrane protectors, frozen protective parts, agricultural coverings, pools and ditches, and gravel for drainage tiles Infiltration barrier.

Use of compounded polymer composition

Another aspect of the invention relates to the use of a polymer composition obtainable by a process comprising the steps of a) providing at least one polylactic acid as a polymer component, and b) providing at least one material comprising calcium carbonate As a filler, and c) providing at least one monosubstituted succinic anhydride d) contacting the components a), b) and c) in any order, and e) compounding the contact components of step d), hygienic products, pharmaceuticals And health care products, filter products, geotextile products, agricultural and horticultural products, clothing, footwear and luggage products, household and industrial products, packaging products, construction products and the like.

According to steps a) to c), at least one polylactic acid is provided as a polymer component, at least one material comprising calcium carbonate as a filler and at least one monosubstituted succinic anhydride as defined above.

According to step d) and step e), the components of a), b) and c) are contacted in any order as defined above and the contacting component of step d) is compounded.

Polymer compositions are used in sanitary products, pharmaceutical and healthcare products, filter products, geotextile products, agricultural and horticultural products, clothing, footwear and luggage products, household and industrial products, packaged products, construction products, and the like.

The following examples are intended to illustrate the invention, but are not intended to limit the invention to the specific examples illustrated.

Example

Measurement method

The parameters given in the examples and the scope of the patent application were evaluated using the following measurement methods.

Particle size distribution of particulate material (mass percentage of particles < diameter X ) and weight median diameter ( d ₅₀ )

As used herein and as is commonly defined in the art, based on the amount determined by measurement using the Sedigraph ^TM 5100 Micromeritics Instrument Company performed "d _50" value-based, and is defined as a particle size, particle size at which, Particles having a diameter equal to the specified value account for 50% (median point) of the mass of the particles.

Methods and apparatus are known to the skilled artisan and are commonly used to determine the particle size of fillers and pigments. The measurement was carried out in an aqueous solution of 0.1 wt% Na ₄ P ₂ O ₇ . Disperse the sample using a high speed agitator and ultrasonic.

BET specific surface area of the material

Throughout this document, the specific surface area (in m ² /g) of the mineral filler is determined using the BET method well known to the skilled person (using nitrogen as the adsorbing gas) (ISO 9277:1995). The total surface area (in m ² ) of the mineral filler is then obtained by multiplying the specific surface area by the mass of the mineral filler before treatment (in g).

Amount of surface treatment layer

The amount of treatment layer on the calcium carbonate containing filler material is theoretically calculated from the BET value of the untreated calcium carbonate containing filler material and the amount of monosubstituted succinic anhydride used for the surface treatment. It is assumed that 100% monosubstituted succinic anhydride added to the filler material containing calcium carbonate is present as a surface treatment layer on the surface of the filler material containing calcium carbonate.

The melt flow rate

The "melt flow rate" was measured on a CEAST melt flow modular pipeline instrument from Instron. Instruments and measurement methods are known to the skilled person. The melt flow rate was measured according to DIN EN ISO 1133-1:2011 by using Procedure A. The polymer sample to be measured is in the form of granules or pellets having a length of from 1 mm to 5 mm. Measured using an amount between 6g and 9g. The sample was measured at 210 ° C using a capillary having an inner diameter of 2.095 mm and a length of 8.00 mm at a nominal load of 2.16 kg. Preheating was carried out without load for 300 seconds and the measurement length was 20 mm.

The melt flow rate was obtained under standard conditions. According to the invention, the term "standard condition" means standard ambient temperature and pressure (SATP), which means a temperature of 298.15 K (25 ° C) and exactly 100000 Pa (1 bar, 14.5 psi, 0.98692 atm). Absolute pressure. All samples that had been stored under similar conditions after preparation were all measured.

Tensile strain at break

The "tensile strain at break" was measured on an Allround Z020 traction device from Zwick Roell. Instruments and measurement methods are known to the skilled person. According to DIN EN ISO 527-2/1BA/50:2012, the tensile strain at break is measured with a preload of 0.1 MPa and a speed of 50 mm/min. The sample of the present invention has a geometric structure of 1 BA, except that the thickness of the sample is between 1.9 mm ± 2 mm and the measured length is 25 mm x 5 mm.

The tensile strain at break was obtained under standard conditions. All samples that had been stored under similar conditions after preparation were all measured.

Material

Filler material containing calcium carbonate

Filler material 1 containing calcium carbonate (powder 1)

Powder 1 was dry ground calcium carbonate from Italy ( d ₅₀ = 2.6 μm, d ₉₈ = 15 μm, BET specific surface area = 2.6 m ² /g).

Filler material 2 containing calcium carbonate (powder 2)

Powder 2 was a dry ground calcium carbonate treated with stearic acid from Italy ( d ₅₀ = 2.6 μm, d ₉₈ = 15 μm, BET specific surface area = 2.6 m ² /g).

Filler material 3 containing calcium carbonate (powder 3)

1.00 kg of dry ground calcium carbonate from Italy ( d ₅₀ = 2.6 μm, d ₉₈ = 15 μm, BET specific surface area = 2.6 m ² /g) was placed in a mixer (Somakon MP-LB Mixer, Somakon Verfahrenstechnik, Germany). The adjustment was carried out by stirring for 10 minutes (2000 rpm, 120 ° C). Thereafter, 0.8 parts by weight of ASA 1 relative to 100 parts by weight of CaCO ₃ was added to the mixture. Stirring was then continued and heating was continued for 20 minutes (120 ° C, 2000 rpm). Thereafter, the mixture was allowed to cool and a free-flowing powder (powder 3) was collected.

Filler material 4 containing calcium carbonate (powder 4)

1.00 kg of dry ground calcium carbonate from Italy ( d ₅₀ = 2.6 μm, d ₉₈ = 15 μm, BET specific surface area = 2.6 m ² /g) was placed in a mixer (Somakon MP-LB Mixer, Somakon Verfahrenstechnik, Germany). The adjustment was carried out by stirring for 10 minutes (2000 rpm, 120 ° C). Thereafter, 0.4 parts by weight of ASA 1 relative to 100 parts by weight of CaCO ₃ was added to the mixture. Stirring was then continued and heating was continued for 20 minutes (120 ° C, 2000 rpm). Thereafter, the mixture was allowed to cool and a free-flowing powder (powder 4) was collected.

Filler material 5 containing calcium carbonate (powder 5)

1.00 kg of dry ground calcium carbonate from Italy ( d ₅₀ = 2.6 μm, d ₉₈ = 15 μm, BET specific surface area = 2.6 m ² /g) was placed in a mixer (Somakon MP-LB Mixer, Somakon Verfahrenstechnik, Germany). The adjustment was carried out by stirring for 10 minutes (2000 rpm, 120 ° C). Thereafter, 1.2 parts by weight of ASA 1 relative to 100 parts by weight of CaCO ₃ was added to the mixture. Stirring was then continued and heating was continued for 20 minutes (120 ° C, 2000 rpm). Thereafter, the mixture was allowed to cool and a free-flowing powder (powder 5) was collected.

Polymer component

Polylactic acid used as a polymer component is commercially available from NatureWorks under the trade name Biopolymer 2003D. The polylactic acid is PDLLA containing 4.6 wt% of the D isomer based on the total weight of the polylactic acid. Further, PDLLA has a specific gravity of 1.24 and a glass transition temperature of 55 ° C to 60 ° C. PDLLA has a residual monomer content of 0.21% by weight based on the total weight of the polylactic acid.

Monosubstituted succinic anhydride

ASA 1

Alkenyl monosubstituted succinic anhydride (dihydromono C _15-20 alkenyl 2,5-furandione derivative, CAS number 68784-12-3) is predominantly branched octadecyl succinic anhydride (CAS #28777- 98-2) Blend with the predominantly branched chain hexadecenyl succinic anhydride (CAS #32072-96-1). More than 80% of the blend is branched chain octadecyl succinic anhydride. The purity of the blend was >95 wt%. The residual olefin content is less than 3% by weight.

Polymer compounding preparation

The compounded polymer composition was prepared in two steps.

In the first step, the polymer component polylactic acid was added to a two-roll mill (Collin 150, Walzwerk 150x400, Germany), and then after the PLA was melted, a filler material containing calcium carbonate was added. The monosubstituted succinic anhydride may be present on the surface of the filler material comprising calcium carbonate and/or may be added separately thereafter. The composition was compounded using a total amount of 120 g of material (filler + polymer + ASA) using the conditions given in Table 1 below.

After obtaining a homogeneous mixture, the melt was removed from the rolls and added again on the roll mill (operation repeated 3 times) for a total compounding time of 11 minutes (unless otherwise specified).

In a second step, the compounded polymer composition is treated in a press (Collin P 300 P, Dr. Collin, Germany). Approximately 90 g of the compounded polymer composition was cut into pieces and pressed between 2 metal plates to obtain a sheet of the following size: 169 x 169 x 2 mm ³ . The pressure program used is given in Table 2 below.

The compounding was carried out in a chamber at 26 ° C ± 2 ° C and 40% to 50% rH.

The amount of material used and the blending of the blended polymer composition are given in Table 3 below.

Melt Flow Rate Analysis of Mixed Polymer Compositions

The melt flow rates of Comparative Example CE1 to Comparative Example CE5 and Inventive Example E1 to Inventive Example E5 are given in Table 4 below. Further, the melt flow rate of pure polylactic acid from the supplier as it is without undergoing the compounding conditions as described above is given in the form of CE6.

As can be seen from the examples, such a reduction can be achieved by using at least one monosubstituted succinic anhydride before or during compounding a polymer composition comprising polylactic acid as the polymer component and at least one material comprising calcium carbonate as the filler. The melt flow rate of the compounded polymer composition. More specifically, the melt flow rate can be reduced to be between 19.9% and 60.4% compared to the same polymer composition that has been treated in the same manner in the absence of at least one monosubstituted succinic anhydride. The measurement results are also graphically presented in Figures 1 and 2.

Tensile tensile strain analysis of compounded polymer composition

The tensile strain at break of Comparative Example CE1 to Comparative Example CE5 and Inventive Example E1 to Inventive Example E5 are given in Table 5 below. All given results are the average of at least 5 tests.

As can be seen from the examples, such an increase can be made by using at least one monosubstituted succinic anhydride before or during compounding a polymer composition comprising polylactic acid as a polymer component and at least one material comprising calcium carbonate as a filler. The tensile strain at break of the compounded polymer composition. More specifically, the tensile strain at break can be increased to be between 118% and 375% compared to the same polymer composition that has been treated in the same manner in the absence of at least one monosubstituted succinic anhydride. The measurement results are also graphically presented in Figure 3.

Claims (23)

Use of at least one monosubstituted succinic anhydride to reduce decomposition of the polymer during processing or prior to compounding a polymer composition comprising polylactic acid as a polymer component and at least one material comprising calcium carbonate as a filler Or as measured according to DIN EN ISO 1133-1:2011 (Procedure A, 2, 16 kg, 210 ° C, granules) compared to the same polymer composition which has been treated in the same manner in the absence of at least one monosubstituted succinic anhydride The melt flow rate of such compounded polymer compositions is reduced by at least 10%. The use according to claim 1, wherein the at least one monosubstituted succinic anhydride is composed of a succinic anhydride monosubstituted by a group selected from the group consisting of an aliphatic group in which it has a carbon of C2 to C30. The total amount of atoms. The use according to claim 2, wherein the aliphatic group is selected from the group consisting of a linear chain, a branched chain, and a cyclic group, wherein the substituent has a C2 to C30, and in the case of a branched chain group , the total amount of carbon atoms from C3 to C30. The use of claim 1 or 2, wherein the at least one monosubstituted succinic anhydride is at least one alkyl monosubstituted succinic anhydride and/or at least one alkenyl monosubstituted succinic anhydride. The use according to claim 4, wherein the at least one alkyl mono-substituted succinic anhydride is at least one alkyl mono-substituted succinic anhydride selected from the group consisting of ethyl succinic anhydride, propyl succinic anhydride, butyl amber Anhydride, triisobutyl succinic anhydride, pentyl succinic anhydride, hexyl succinic anhydride, heptyl succinic anhydride, octyl succinic anhydride, decyl succinic anhydride, decyl succinic anhydride, dodecyl succinic anhydride, hexadecyl succinic anhydride, Octadecyl succinic anhydride and mixtures thereof. The use according to claim 4, wherein the at least one alkenyl mono-substituted succinic anhydride is at least one alkenyl mono-substituted succinic anhydride selected from the group consisting of vinyl succinic anhydride, acryl succinic anhydride, butenyl Succinic anhydride, triisobutenyl succinic anhydride, pentenyl succinic anhydride, hexenyl succinic anhydride, heptenyl succinic anhydride, octenyl succinic anhydride, nonenyl succinic anhydride, nonenyl succinic anhydride, dodecenyl amber Anhydride, hexadecenyl succinic anhydride, octadecyl succinic anhydride, and mixtures thereof. The use of claim 1 or 2, wherein the at least one monosubstituted succinic anhydride is used prior to compounding the polymer composition because the at least one monosubstituted succinic anhydride and/or its salt-containing reaction product Present on the surface of the at least one material comprising calcium carbonate. The use of claim 1 or 2, wherein the at least one monosubstituted succinic anhydride is used during compounding of the polymer composition because the at least one monosubstituted succinic anhydride is mixed with polylactic acid as The polymer component and at least one material comprising calcium carbonate are contacted as the filler of the polymer composition. The use of claim 1 or 2, wherein the at least one monosubstituted succinic anhydride and/or its salt-containing reaction product is 0.1 wt% based on the total dry weight of the at least one filler material comprising calcium carbonate. An amount of from % to 4.0% by weight is present in the polymer composition. The use of claim 1 or 2, wherein the polymer component consists solely of polylactic acid. The use of claim 1 or 2, wherein the at least one monosubstituted succinic anhydride and/or its salt-containing reaction product is present in an amount of at least 0.005 wt% based on the total weight of the polymer component. In the polymer composition. The use of claim 11, wherein the at least one monosubstituted succinic anhydride and/or its salt-containing reaction product is present in an amount of 0.01% by weight to 5.0% by weight based on the total weight of the polymer component. In the polymer composition. The use of the calcium carbonate-containing material is selected from the group consisting of ground calcium carbonate; precipitated calcium carbonate; and mixtures thereof, as claimed in claim 1 or 2. The use of the invention of claim 12, wherein the ground calcium carbonate is selected from the group consisting of marble, limestone, dolomite and/or chalk; the precipitated calcium carbonate is selected from the group consisting of hexagonal calcite, calcite and/or aragonite. The use of the material of claim 1 or 2, wherein the material comprising calcium carbonate has i) a weight median particle diameter d ₅₀ value in the range of 0.1 μm to 10 μm; and/or ii) Top cut of 15μm (d _98); and / or iii) in accordance with ISO 9277: 2010 using nitrogen and the BET method of measuring, 0.5m ² / g to 150m ² / g of specific surface area (BET); and / or iv And a residual total water content of from 0.01% by weight to 1% by weight based on the total dry weight of the at least one material comprising calcium carbonate. The use of the first or second aspect of the patent application, wherein the material comprising calcium carbonate is present in the polymer composition in an amount of from 0.1% by weight to 85% by weight based on the total weight of the polymer component. The use of claim 1 or 2, wherein the polymer composition comprises other additives such as colored pigments, dyes, waxes, lubricants, oxidative stabilizers and/or UV stabilizers, antioxidants, and the like. A filler from talc. The use of claim 1 or 2, wherein the polymer composition has an increase in tensile strain at break of at least 40% compared to the same polymer composition lacking at least one monosubstituted succinic anhydride. The use of the first or second aspect of the patent application, which is measured according to DIN EN ISO 1133-1:2011 (procedure A, 2, 16 kg, 210 ° C, granules), and the absence of at least one monosubstituted succinic anhydride The melt flow rate of the polymer composition is reduced by at least 15% compared to the same polymer composition. A method for reducing decomposition of the polymer during processing and/or measuring according to DIN EN ISO 1133-1:2011 (procedure A, 2, 16 kg, 210 ° C, particles), and lack of at least one monosubstituted succinic anhydride Decreasing the melt flow rate of a polymer composition comprising polylactic acid as a polymer component and at least one material comprising calcium carbonate as a filler by at least 10% compared to the same polymer composition treated in the same manner The method comprises a) providing at least one polylactic acid as a polymer component, and b) providing at least one material comprising calcium carbonate as a filler, and c) providing at least one monosubstituted succinic anhydride d) such that a), b) And the components of c) are contacted in any order, and e) the contacting components of step d) are compounded. The method of claim 20, wherein in the contacting step d), the at least one material comprising the calcium carbonate of the step b) is first combined with the at least one of the step c) in one or more steps with mixing Contacting the monosubstituted succinic anhydride such that a treatment layer comprising the at least one monosubstituted succinic anhydride and/or its salt-containing reaction product is formed on the surface of the at least one material comprising calcium carbonate of step b), and secondly under mixing Make this surface treated include The calcium carbonate material is contacted with the polylactic acid in one or more steps. Use of a polymer composition obtainable by a process comprising the steps of a) providing at least one polylactic acid as a polymer component, and b) providing at least one material comprising calcium carbonate as a filler, and c) providing at least one single Substituting succinic anhydride d) contacting the components of a), b) and c) in any order, and e) compounding the contact components of step d) for use in sanitary products, pharmaceuticals And health care products, filter products, geotextile products, agricultural and horticultural products, clothing, footwear and luggage products, household and industrial products, packaging products, construction products and the like. An article comprising a polymer composition, the polymer composition being obtainable by a method comprising the steps of: a) providing at least one polylactic acid as a polymer component, and b) providing at least one material comprising calcium carbonate as a filler, and c) providing at least one monosubstituted succinic anhydride d) contacting the components of a), b) and c) in any order, and e) compounding the contacting components of step d), wherein the product is selected It includes the following groups: hygiene products, pharmaceutical and health products, filter products, geotextile products, agricultural and horticultural products, clothing, footwear and luggage products, household and industrial products, packaging products, construction products and the like.